$É5 り s ^ { ~ Ä ¼ Ü ¨ Ú ä a![(ê ![(ê) : l º...¨ Û Ü é b o ¢ (ê é "8 a : * [...
TRANSCRIPT
㈻
り
㈻
り
┘
1
り
11
14
26
41
り
43
48
53
59
61
1
さ 2┊
㈻
1) 2 [PtCl3(H2C=CH2)]– d-
cis-[PtCl2(NH3)2] み 2 DNA
り よ
り り
り
㈻ ㈻り
◢
0, +2, +4り
Ⅴ 1769 Υ Ⅴ
100 ㈻ り さ ┊
ふⅤ
り ぜ
り Lewis-Lewis
10 0
さ d 9, 10 4, 56
り り
さ り
オ り
り り
り
り
さ (Eqs. 1, 2) 2b, c)
2
H2PtCl6 / i-PrOH
H2SiCl2
SiHCl2
(1)+neat, 55 °C
82%
SiCl3SiCl3
+ (2)H2PtCl6 / i-PrOH
neat, reflux72% 20%
HSiCl3+
り
り H2PtCl6: Speier り 3) Karstedt り [Pt2{(H2C=CHSiMe2)2O}3] 0 4 )
┞ 4b, c, d) り
セ 1 ppm り
Ⅴ ┊ り さ
DMSO ┞
, -り 5 )
り Chalk-Harrod (Scheme 1) 6) 4 2
り
PtII/Pt0
Pt(PH3)2
ゝ
よ 7) Chalk-Harrod8)
3
Scheme 1
Pt
Cl
Cl
Cl Cl
ClCl
PtCl
Cl Cl
Cl
PtCl
Cl
Cl
R'
Pt
H
Cl
Cl
SiR3Cl
R'
Pt
Cl
Cl
Cl
SiR3Cl
H
R'
R'SiR3
R'
HSiR3
R'
2–
2–
(HSiR3)
2–
Cl
Cl
+ Cl
i-PrOH IIIV
II
IVIV
–
–
–
–
–
り
り 9) り
( )
り10a)
り り11 ) り 12)
り 13, 14)
り り さ
さ (Eqs. 3, 4) 13b, 13c) り
り
り
(Eq. 5) 14d)
14e)
4
SiMe2
SiMe2
E E
(E = CO2Me)
SiMe2
Me2Si E
E
Si
Si
E
E
E
E
Me2
Me2
+ (3)
PdCl2(PPh3)4PdCl2(PhCN)2
Pt(H2C=CH2)(PPh3)2
68%
30%
71%
18%
47%
-
SiMe2X
SiMe2X
SiMe2X
SiMe2X
+Pt(PPh3)4
(4)
O
B
O O
B
O
Bu
Bu H
B BO
O O
O
Bu H
B PhO
O
Bu
Ph
H
Bu
+Pt(PPh3)4
Pd(PPh3)4
PhX Bu Br
Pd(PPh3)4 / Base
(5)
(r.t.)
(r.t.)
(reflux)
benzene
benzene, 150 °C(5 atm)
DMF, 80 °C
2Lewis り
Diels–AlderLuo 2
(Eq. 6) 15c)
∞
Diels–Alderば LUMO
(Eq. 7) 15d)
H
O
O
Ph
(BIPHEP)Pt[(S)-BINOL]
AgOTf
O O
H Ph
PtPh2P PPh2
!
OH
O
Ph+
2+
(6)CH2Cl2, r.t.
73%, 94%ee
+
O
N O
O
O
N O
O
Ph2PPt
PPh2H
O NO
O
2+
(7)
CH2Cl2, –78 °C
[(R)-BINAP]Pt(SbF6)2
99%yield
endo/exo = 97:3, 98%ee
Lewis -Lewis
5
16) Trostり 1,6- (Eq. 8)
17) (Ph3P)2Pt(OAc)2 り
さ (Eq. 9) 17d) り 1,6-ぜ (Eq. 10) 18)
-Lewis 2 18-23)
(Eq. 11) 19)
(Eq. 12) 20)
(Eq.13) 21)
Pd (8)
–
E = CO2R
E
E
E
E
Pd
E E
E EPd
E E
E E
MeO2C O PhMeO2C
O Ph(Ph3P)2Pt(OAc)2
1.3 eq. CF3CO2H
2.1 eq. DMAD
(9)
XX
PtCl2
X X
Cl2Pt
cat. PtCl2(10)
X
SiMe3
cat. PtCl2
X
PtCl2SiMe3
X
(11)
X
R1
X
PtCl2
R1
X
R1
OR2
cat. PtCl2(12)
R2OH
X
X
cat. PtCl2
X
R1
Cl2Pt
X
Cl2Pt
X
R1X
X
R1(13)
X
6
り Wackerり 2 -Lewis
り24)
り - り 25)
㌹ ㈻
り
(Eq. 14) 26) り
り (Eq. 15) 27) り
り (Eq. 16) 28)
OO
OO
OO5 mol% PdCl2(MeCN)22.5 eq. CuCl2
1 mol% [PtCl2(H2C=CH2)]22 mol% EuCl3
(14)
!-H Elimination
Protonation
NMe
NMe
[PtCl2(H2C=CH2)]2(15)
NMe
PtCl2
NMe
NMe
Pd(OAc)2
pyridine ligand / O2
(16)
NMe
PdLn
り
- 2 (Eqs. 17, 18) 29)
り り
-
り
7
OH
SiR ( )n
cat. L
n = 1, 2
Si = SiMe2R
OH
SiR ( )n
L protontransfer OL
SiR ( )n
– L O
RSi
( )n
(17)
NHP
SiR ( )n
cat. L
n = 1, 2
Si = SiMe2R
NHP
SiR ( )n
L protontransfer NPL
SiR ( )n
PN
RSi
( )n
(18)– L
り Lewis-Lewis
り
(Eq. 19) 30)
Prins り
Prins Lewis
OH
SiMe3
( )n
cat. PtCl2-2AgX
(X= OTf, SbF6)
n = 1, 2
Si = SiMe2R
(19)
OH
SiMe3
( )n
OR1R1CHO ( )n
㈻
(Scheme 2) 31)
(R´ � � = H) (R´ � = (CH2)4C(Me)=CH2)
Scheme 2
OH
O
R OR'
O
R OR'O R
O R
Isomerization
cyclization
! R'OH
! Hcat. PtX2
RCHO
cat. PtX2-2AgOTf
RCHO
R' = H or (CH2)4C(CH3)=CH2
X = OTf, SbF6
H
8
Lewis -Lewis 2 り
┘ り
(Scheme 3)
Scheme 3
R SiMe3
R1
OSiMe3
R1
OMe
R1
OMe
R
Ph
Ph
R
cat. PtCl2-2LiI
cat. PtCl2-2AgX
(X = OTf, SbF6)
R
PtX
R SiMe3
R1CHO
R1CH(OMe)2
R1CH(OMe)2
Ph2CHOR2
R
R
2 り
り Eq. 19┘
り
り
❻ (Eq. 20)
ふⅤ
R SiMeOH+
cat. Pt
RPt
ROMe (20)
16%
9
1) (a) Peloso, A. Coord. Chem. Rev. 1973, 10, 123. (b) Basolo, F.; Chatt, J.; Gray, H. B.; Pearson, R. G.;
Shaw, B. L. J. Chem. Soc. 1961, 2207. (c) Belluco, U.; Cattatini, L.; Basolo, F.; Pearson, R. G.; Turco, A. J. Am. Chem. Soc. 1965, 87, 241.
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3) (a) Speier, J. L. Adv. Organomet. Chem. 1979, 17, 407. (b) Speier, J. L.; Webster, J. A.; Barnes, G. H. J. Am. Chem. Soc. 1957, 79, 974.
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5) (a) Lewis, L. N.; Sumpter, C. A.; Davis, M. J. Inorg. Organomet. Polym. 1995, 5, 377. (b) Lewis, L. N.; Sumpter, C. A.; Stein, J. J. Inorg. Organomet. Polym. 1996, 6, 123. (c) Lewis, L. N.; Stein, J.; Colborn, R. E.; Gao, Y.; Dong, J. J. Organomet. Chem. 1996, 521, 221.
6) Chalk, A. J.; Harrod, J. F.; J. Am. Chem. Soc. 1965, 87, 16. 7) Sakaki, S.; Ieki, M. J. Am. Chem. Soc. 1993, 115, 2373. 8) (a) Lewis, L. N.; Lewis, N. J. Am. Chem. Soc. 1986, 108, 7228. (b) Lewis, L. N.; Uriarte, R. J.; Lewis, N.
J. Catalysis 1991, 127, 67. (c) Faglioni, F.; Blanco, M.; Goddard, W. A. III.; Saunders, D. J. Phys. Chem. B 2002, 106, 1714.
9) (a) Marciniec, B. Silicon Chemistry 2002, 1, 155. (b) Kuhnen, T.; Stradiotto, M.; Ruffolo, R.; Ulbrich, D.; McGlinchey, M. J.; Brook, M. A. Organometallics 1997, 16, 5042. (c) Lewis, L. N.; Uriarte, R. J. Organometallics 1990, 9, 621.
10) (a) Guliński, J.; James, B. R. J. Mol. Catal. 1992, 72, 167. (b) Sakaki, S.; Mizoe, N.; Sugimoto, M. Organometallics 1998, 17, 2510.
11) (a) Onopchenko, A.; Sabourin, E. T.; Beach, D. L. J. Org. Chem. 1983, 48, 5101. (b) Onopchenko, A.; Sabourin, E. T.; Beach, D. L. J. Org. Chem. 1984, 49, 3389. (c) Ojima, I.; Fuchikami, T.; Yatabe, M. J. J. Organomet. Chem. 1984, 260, 355. (d) Süss-Fink, G.; Reiner, J. J. Mol. Catal. 1982, 16, 231. (e) Seki, T.; Takeshita, K.; Kawamoto, K.; Murai, S.; Sonoda, N. Angew. Chem., Int. Ed. Engl. 1980, 19, 928. (f) Christ, M. L.; Sabo-Etienne, S.; Chaudret, B. Organometallics 1995, 14, 323.
12) Svododa, P.; Sedlmayer, P.; Hetflejs, J.; Coll. Czech. Chem.Commun. 1973, 38, 1783. 13) (a) Suginome, M.; Ito, Y. Chem. Rev. 2000, 100, 3221. (b) Kusukawa, T.; Kabe, Y.; Nestler, B.; Ando, W.
Organometallics 1995, 14, 2556. (c) Hayashi, T.; Kobayashi, T.-a.; Kawamoto, A. M.; Yamashita, H.: Tanaka, M. Organometallics 1982, 9, 280. (d) Watanabe, H.; Kobayashi, M.; Higuchi, K.; Nagai, Y. J. Organomet. Chem. 1980, 186, 51.
14) (a) Beletskaya, I.; Moberg, C. Chem. Rev. 1999, 99, 3435. (b) Ishiyama, T.; Matsuda, N.; Miyaura, N.; Suzuki, A. J. Am. Chem. Soc. 1993, 115, 11018. (c) Ishiyama, T.; Matsuda, N.; Murata, M.; Ozawa, F.; Suzuki, A.; Miyaura, N. Organometallics 1996, 15, 713. (d) Ishiyama, T.; Yamamoto, M.; Miyaura, N. Chem. Lett. 1996, 1117. (e) Cui, Q.; Musaev, D. G.; Morokuma, K. Organometallics 1997, 16, 1355. (f) Lesley, G.; Nguyen, P.; Taylor, N. J.; Marder, T. B.; Scott, A. J.; Clegg, W.; Norman, N. C. Organometallics 1996, 15, 5137. (g) Iverson, C. N.; Smith, M. R. III Organometallics 1996, 15, 5155.
15) (a) Kündig, E. P.; Saudan, C. M. In Lewis Acids in Organic Synthesis, Vol. 2; Yamamoyo, H., Ed.;
10
Wiley-VCH: Weinheim, 2000, 597. (b) Fujimura, O. J. Am. Chem. Soc. 1998, 120, 10032. (c) Luo, H.-K.; Schumann, H. J. Mol. Catal. A. 2006, 248, 42. (d) Ghosh, A. K.; Matsuda, H. Org. Lett. 1999, 1, 2157. (e) Brunkan, N. M.; White, P. S.; Gagné, M. R. Organometallics 2002, 21, 1565. (f) Brunkan, N. M.; White, P. S.; Gagné, M. R. Organometallics 2002, 21, 1576. (g) Oi, S.; Terada, E.; Ohuchi, K.; Inoue, Y. J. Org. Chem. 1999, 64, 8660. (h) Nishibayashi, Y.; Yoshikawa, M.; Inada, Y. Milton, M. D.; Hidai, M.; Uemura, S. Angew. Chem. Int. Ed. 2003, 42, 2681.
16) (a) Chisholm, M. H.; Clark, H. C. Acc. Chem. Res. 1973, 6, 2681. (b) Belluco, U.; Bertani, R.; Michelin, R. A.; Mozzon, M. J. Organomet. Chem. 2000, 600, 37.
17) (a) Trost, B. M.; Tanoury, G. J. J. Am. Chem. Soc. 1988, 110, 1638. (b) Trost, B. M.; Trost, M. K.. J. Am. Chem. Soc. 1991, 113, 1850. (c) Trost, B. M.; Yanai, M.; Hoogsteen, K. J. Am. Chem. Soc. 1993, 115, 5294. (d) Trost, B. M.; Chang, V. K. Synthesis 1993, 824.
18) (a) Chatani, N.; Morimoto, T.; Muto, T.; Murai, S. J. Am. Chem. Soc. 1994, 116, 6049. (b) Chatani, N.; Furukawa, N.; Sakurai, H.; Murai, S. Organometallics 1996, 15, 901.
19) Fernández-Rivas, C.; Méndez, M.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 1221. 20) Méndez, M.; Muñoz, M. P.; Echavarren, A. M. J. Am. Chem. Soc. 2000, 122, 11549. 21) (a) Chatani, N.; Kataoka, K.; Murai, S.; Furukawa, N.; Seki, Y. J. Am. Chem. Soc. 1998, 120, 9104. (b)
Chatani, N.; Inoue, H.; Ikeda, T.; Murai, S. J. Org. Chem. 2000, 65, 4913. 22) (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305. (b) Fürstner, A.;
Stelzer, F.; Szillat, H. .; Méndez, M.; Echavarren, A J. Am. Chem. Soc. 2001, 123, 11863. (c) Fürstner, A.; Davies, P. W.; Gress, T. J. Am. Chem. Soc. 2005, 127, 8224.
23) Oi, S; Tsukamoto, I.; Miyano, S.; Inoue, Y. Organometallics 2001, 20, 3704. 24) (a) Chianese, A. R.; Lee, S. J.; Gagné, M. R. Angew. Chem. Int. Ed. 2007, 46, 4042. (b) Haan, C. Chem.
Eur. J. 2004, 10, 5888. 25) Lersch, M.; Tilset, M. Chem. Rev. 2005, 105, 2471. 26) (a) Widenhoefer, R. A. Pure. Appl. Chem. 2004, 76, 671. (b) Widenhoefer, R. A.; Liu, C. Tetrahedron.
Lett. 2005, 46, 285. (c) Yang, D.; Li, J.-H.; Gao, Q.; Yan, Y.-L. Org. Lett. 2003, 5, 2869. 27) Liu, C.; Han, X.; Wan, X.; Widenhoefer, R. A. J. Am. Chem. Soc. 2004, 126, 3700. 28) Ferreira, E. M.; Stoltz, B. M. J. Am. Chem. Soc. 2003, 125, 9578. 29) (a) Miura, K.; Okajima, S.; Hondo, T.; Hosomi, A. Tetrahedron. Lett. 1995, 36, 1483. (b) Miura, K.;
Hondo, T.; Okajima, S.; Hosomi, A. Tetrahedron. Lett. 1996, 37, 487. (c) Miura, K.; Okajima, S.; Hondo, T.; Nakagawa, T.; Takahashi, T.; Hosomi, A. J. Am. Chem. Soc. 2000, 122, 11348. (d) Miura, K.; Hondo, T.; Nakagawa, T.; Takahashi, T.; Hosomi, A. Org. Lett. 2000, 2, 385. (e) Miura, K.; Takahashi, T.; Nishikori, H,; Hosomi, A. Chem. Lett. 2001, 958.
30) Miura, K.; Itaya, R.; Horiike, M.; Izumi, H.; Hosomi, A. Synlett. 2005, 3148. 31) Miura, K.; Horiike, M.; Inoue, G.; Ichikawa, J.; Hosomi, A. Chem. Lett. in press.
11
り
さ
1990 5よ
さ ㌹ (Eq. 1)
┘ (Eq. 2) 1)
NaOH NaCl+ + (1)
O
Cl OH
cat. Li3PO4OH (2)
ぜ
(Riley ) 1,3-Prins -Baylis-Hillman
り り
(Eq. 3) 2) ┘ palytoxin (Figure 1) 3)
↓4)
Figure 1.
O
H2N OH
O
O
OH
OH
O
HO OH
OH OH
OH OH
Me
OH
HO
HO
OH
O
OH
OH
OH
O
HO
OH
HO
OH
OH
OH
Me
OOH
OHOH
OH
OH
HOHO
OO
Me
MeMe OH
HOOH
OH
OOH
OH
OHHO
NH
MeO HOOH
OH
Me
OH
O
NH
HO
palytoxin
12
R1X
cat. NiCl22 eq. CrCl2
R1NiX
R1CrX2
CrX3
- NiX2 R1 OH
R2 R3R2
O
R3
(3)
0 り
Montgomery (Eq. 4) 5) Jamison3 (Eq.
5) 6) モ さ
Ⅴ
R1 H +R2
O
H
O
LNi
R1
H R2phosphine ligand
cat. Ni(cod)2 R32Zn OH
R2R1(4)
R3
R1
R2
O
H
R3SiOTfcat. Ni(cod)2
phosphine ligand
O
LNi
R1 R2
OSiR3
R2
R1
+ + (5)R3SiOTf
Et3N
ふⅤ り
-, - (Eq. 6) 7)
- り
(Eq. 7) 8)
R2
R1
SiMe3
R3EX-AlCl3
" E "
R2R1
ER3
R2
R1
E
R3SiMe3
(6)
EX = RCCl, ROCH2Cl, etc.
O
C !-Silylcarbenium Ion
R2
R1
SiYMe2
R3ArX-cat.Pd(0)
" Ar-Pd-X "
F R2
R1
PdAr
R3
R2
R1
Ar
R3
Y = OR, F, etc. Vinylpalladium
(7)
(Eq. 8) 9) り
(cine ) (Eq. 9) 10)
13
OX OO
SiMe3 SiMe3
Lewis Acid+
traceX = MEM, MOM, CH2Cl
(8)
H
Ar1
SiMe3
H
Ar2N2BF4+cat. Pd(OAc)2
H
Ar1
Ar2
H
Ar2
Ar1
H
H
+ (9)
22 り
(Eq. 10) 11)
Prins
┘
(Scheme 1)
OH
SiMe3
( )n
cat. PtCl2-2AgX
(X= OTf, SbF6)
n = 1, 2
Si = SiMe2R
(10)
OH
SiMe3
( )n
OR1R1CHO ( )n
Scheme 1
R SiMe3cat. Pt (II)
R SiMe3
? Ph
OSiMe3
Ph
OSiMe3
R
R
PhCHO
PhCHO
14
1a
2 (Z)- 1a 1,2- (DCE) り
(10 mol%) 2a 13% (Entry 1 in Table 1)
(THF) 1,2- (DME) (Entries 2–4)
(CuCl2, NiCl2, PdCl2, RhCl3, IrCl3, AuCl3, [RhCl(cod)]2 ) り
┘
0 り (Entries 6 and 7) DCE 々
(Entry 8) (Entries 9–12) り
々
┘ (Entry 13) DCE り
(Entry 16) DME り
(Entry 17) (Entries 18 and 19)
り (Entries 20–25)
2a (Entry 25)
(Entries 12 and 26) り ┘
1a
(Table 2) ┘
2 (Entries 3, 4, 7–11) 4- 4-
(Entries 5 and 6) 2 (Entries 7–11) 2-
4-
2 々 2 (Entries 12–15) 4-
24 2 (Entry 16) ├
2 (Entry 17)
15
2 (Entries 18 and 19) (Entry 20) , -
(Entries 21 and 22)
Table 1. Optimization of Reaction Conditions
n-C10H21 SiMe3Ph
O
HPh
OSiMe3
n-C10H21
Catalyst (10 mol%)
Additive (20 mol%)
70 °C, 24 h
+ + Ph
OH
n-C10H211a (2 eq.)
2a alcohol Yield / %
Entry Catalyst Additive Solvent 2a alcohol
1 PtCl2 - (CH2Cl)2 13 1
2 PtCl2 - THF 10 7
3 PtCl2 - diglyme 15 3
4 PtCl2 - (CH2OMe)2 24 <3
5 PtCl2 - AcOEt 16 <1
6 Pt(PPh3)4 - (CH2Cl)2 0 0
7 Pt(dba)2 - (CH2Cl)2 0 0
8 PtCl4 - (CH2Cl)2 <37 <4
9 PtCl2(COD) - (CH2Cl)2 0 0
10 cis-PtCl2(PPh3)2 - (CH2Cl)2 0 0
11 (2,2-bipyridine)PtCl2 - (CH2Cl)2 1 0
12 cis-PtCl2(PhCN)2 - (CH2Cl)2 10 0
13 PtCl2 AgOTf (CH2Cl)2 0 0
14 PtBr2 - (CH2Cl)2 <12 trace
15 PtBr2 - (CH2OMe)2 trace trace
16 PtI2 - (CH2Cl)2 70 <1
17 PtI2 - (CH2OMe)2 0 0
18 PtI4 - (CH2Cl)2 46 4
19 PtI4 - (CH2OMe)2 24 <10
20 PtCl2 AgI (CH2Cl)2 4 0
21 a PtCl2 KI (CH2Cl)2 28 0
22 PtCl2 KI (CH2Cl)2 77 <10
23 a PtCl2 NaI (CH2Cl)2 39 0
24 PtCl2 NaI (CH2Cl)2 65 3
25a PtCl2 LiI (CH2Cl)2 82 0
26b cis-PtCl2(PhCN)2 LiI (CH2Cl)2 26 trace aThe reaction time is 2 h. bThe reaction time is 12 h.
16
Table 2. Pt-Catalyzed Reaction with Various Aldehydes
n-C10H21 SiMe3R
O
HR
OSiMe3
n-C10H21
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)270 °C
+
1a (2 eq.)2
Entry R Time / h Product Yield / %
1 Ph 2 2a 82
2 1-Naphthyl 24 2b 84
3 4-O2N-C6H4 24 2c 84
4 4-MeO2C-C6H4 48 2d 77
5 4-NC-C6H4 48 2e 45
6 4-Ac-C6H4 48 2f 28
7 4-F-C6H4 24 2g 89
8 4-Cl-C6H4 5 2h 90
9 2-Cl-C6H4 48 2i 86
10 4-Br-C6H4 48 2j 91
11 4-I-C6H4 36 2k 71
12 4-Me-C6H4 5 2l 58
13 4-Me-C6H4 24 2l <19
14 4-MeO-C6H4 2 2m 18
15 4-MeO-C6H4 24 2m 0
16 4-AcO-C6H4 24 2n 69
17 n-C6H13 5 - 0
18 Et2CH 2 2o 13
19 c-C6H 11 5 2p 38
20 t-Bu 24 - 0
21 PhCH=CH 2 - 0
22 H2C=CHMe 24 2q 7
1a 4-
1a 4- (Entries 1 and 2 in Table 3)
2
(Entries 3 and 4) 4 Ⅴ
2 24 々
2┘ 2 24
(Entry 5) THF 々
(Entry 6) (Entry 7)
17
(Entry 9) DMF ┘
(Entries 10 and 11)
Table 3. Reaction of 4-Methoxybenzaldehyde
n-C10H21 SiR3
O
H
OSiR3
n-C10H21
Catalyst (10 mol%)
Additive
70 °C
+
1 (2 eq.)2
MeO MeO
Entry Catalyst Additive R Solvent Time / h Yield / %
1 PtCl2 LiI (20 mol%) Me (CH2Cl)2 2 18
2 PtCl2 LiI (20 mol%) Me (CH2Cl)2 24 0
3 PtCl2 LiI (20 mol%) Et (CH2Cl)2 4 13
4 PtCl2 LiI (20 mol%) Et (CH2Cl)2 24 0
5 PtCl2 – Me (CH2Cl)2 24 5
6 PtCl2 – Me THF 24 <40
7 PtCl2 LiI (20 mol%) Me THF 24 0
8 PtI2 – Me THF 24 <18
9 PtCl2 K2CO3 (1.0 eq.) Me THF 24 9
10 PtCl2 – Me MeCN 24 0
12 PtCl2 – Me DMF 24 0
4 24 (Eq. 11) り 2m
42a 4-
n-C10H21 SiMe3Ph
O
H
Ph
OSiMe3
n-C10H21
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)2
70 °C, 24 h
+
1a (2 eq.)
2a, 2%
+
O
H
MeO
Ph
O
H
+
O
H
MeO
+
OSiMe3
n-C10H21
+
MeO2m, 0%92% 71%
(11)(1 eq.) (1 eq.)
GC Yield
1a
(Eq. 12)
(Table 4)
18
OSiMe3
H
Me3SiI
– HI
O
H (12)
┘ 2p (Entries 1 and 2) ┘
2p (Entries 3 and 4)
┘ (Entries 5, 6) ┘
Lewis さ
2p (Entry 12) Lewis
(Entries 17 and 18) (Entry 19)
Table 4. Pt-Catalyzed Reaction with Cyclohexanecarbaldehyde
n-C10H21 SiMe3
O
H
OSiMe3
n-C10H21
PtCl2 (10 mol%)
MIn
(CH2Cl)2
70 °C, 4 h
+
1a (2 eq.)2p
Entry MIn mol% Yield / % Entry MIn mol% Yield / %
1a LiI 20 38 11 TiI4 10 0
2 LiI 10 57 12 MnI2 10 71
3 LiI 5 31 13 FeI2 10 56
4 - - 2 14 NiI2 10 7
5 NaI 20 63 15 a ZnI2 10 0
6 NaI 10 69 16 InI3 10 0
7 KI 20 14 17 CeI3 10 43
8 CsI 10 6 18 SmI3 10 14
9 a MgI2 10 48 19 b , c PtI2 10 67
10 CaI2 10 27 aThe reaction time is 5 h. bThe reaction time is 24 h. cWithout PtCl2.
2-
19
n-C10H21 SiMe3
O
H
OSiMe3
n-C10H21
PtCl2 (10 mol%)
MIn (10 mol%)
(CH2Cl)2, 70 °C+
1a (2 eq.)2o
13%
14%
30%
LiI*
NaI
MnI2
(2 h)
(4 h)
(2 h)
(13)
*20 mol%
(Table 5) 1a ((E)-1a) モ Z
り (Entry 2) 1b (Entry 3)
1c 1d┘ (Entries 4 and 5)
1e (Entry 6) 1d
(Entries 7 and 8) 1f 1f
々 (Entry 7) 1g
(Entry 8) t-1h 1i 1j
(Entries 9–11)
1b 4-
り ┘
(Eq. 14)
Me SiMe3
PtCl2 (5 mol%)
LiI (10 mol%)
(CH2Cl)2
70 °C, 24 h1b (2 eq.)
+
O
H
Cl
OSiMe3
MeCl
2r', 91%
(14)
20
Table 5. Pt-Catalyzed Reaction of Various Vinylsilanes with Benzaldehyde
R SiPh
O
HPh
OSi
R
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)270 °C
+
1 (2 eq.)2
Entry Vinylsilane R Si Time / h Product Yield / %
1 1a n-C10H21 SiMe3 2 2a 82
2 (E)-1a n-C10H21 SiMe3 24 2a 60
3 1b Me SiMe3 2 2r 78
4 1c H SiMe3 2 - 0
5 1d c-C6H 11 SiMe3 24 2s 5
6 1e Ph SiMe3 10 2t 69
7 1f 4-MeO-C6H4 SiMe3 2 - C.M.
8 1g 4-CF3-C6H4 SiMe3 24 2v 6
9 1h n-C10H21 SiMe2tBu 24 2w 29
10 1i n-C10H21 SiMe2Ph 10 2x 60
11 1j n-C10H21 SiEt3 10 2y 82
1a
4 (Eqs. 15 and 16) 4-2h
3b 4b1a
R
OMe
OMeR
OSiMe3
n-C10H21
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)2, 70 °C+
1a (2 eq.)
R
OMe
n-C10H21
R
OMe
n-C9H19
+ +
2a, 0%
2h, 41%
3a, 26%
3b, 29%
4a, 3%
4b, 11%
R = Ph (2 h)
R = 4-Cl-C6H4 (24 h)
(15)n-C10H21 SiMe3
as above
24 h
+1a (2 eq.)Ph
O
n-C10H21
Ph
O
n-C9H19
+
3c, 33% 4c, 4%
O
O
Ph
OSiMe3 OSiMe3
(16)
, - 55´ (Eqs. 17 and 18) 5´ �
5´ �
21
OO
n-C10H21
O n-C10H21+
1a (2 eq.)
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)270 °C, 24 h
+ (17)
5a, 15% 5a', 10%
n-C10H21 SiMe3
+1a (2 eq.)
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)2
70 °C, 24 h
+ (18)
5b, 2% 5b', 1%
OO
n-C10H21
O
n-C10H21
Scheme 26
67 1,2-
2 Lewis
Scheme 2. A Possible Mechanism
R1 Si R2
SiO PtX2
R1 H
R2
SiO PtX2
R1 H
R'2
SiO PtX2
R1
H
R2
SiO
R1
PtX2 R'CHO
R1PtX
– PtX2Si = SiR3
X = Cl, I
SiX+
61
7
7'
2
Noels り
ぜ (Eqs. 19 and 20) 12)
り 1aよ ❻ 8 (Eq.
21) (Eq. 22) 8
6 13) 9 (Scheme 3) 8 Scheme 2
22
ROH N2CHCO2Et
H
LnPt
CO2Et
H
LnPt
CO2Et
RO-CH2CO2Et+ROH
OH N2CHCO2Et OCH2CO2Et
OO
HCO2Et
HHOH2C
+ + +cat. Pt
(19)
(20)cat. Pt
n-C10H21 SiMe3n-C10H21
OMePtCl2 (5 mol%), LiI (10 mol%)
MeOH-(CH2Cl)2 (1:1)
70 °C, 24 h 8. 16%1a
(21)
n-C10H21
OMeas above
MeOD-(CH2Cl)2 (1:1)
8-D. 15%
1a
(85%D) D
D (>99%D)
(22)
Scheme 3
RPtX
R = n-C10H21, Si = SiMe3, X = Cl, I
RPtX2SiX+
MeOH
– MeOSi96
1a
PtX2
– PtX2
8
MeOH
7 1,2-1a-D
モ ❻ ㎲
(Eq. 23) 1,2-
n-C10H21 SiMe3 Ph
O
HPh
OSiMe3
n-C10H21
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)270 °C, 4 h
+
1a-D (2 eq., 92%D) 2a-D, 87% (86%D)
D
D (23)
Scheme 2 ッ
1b 1i り
2r 2r´ � 2x 2a 1 : 1
2r 2x (Eq. 24) 2r´ � 2a 1b 1i
1a-D 1k (Eq. 25)
23
6´ �さ (Scheme 4) 6´
Me SiMe3Ph
O
H
Ph
OSiMe3
Me
+
+ Ph
OSiMe2Ph
Me
1b (1 eq.)
2r 2r'
+ n-C10H21 SiMe2Ph
PtCl2 (10 mol%)
LiI (20 mol%)
(CH2Cl)2
70 °C, 4 h
+ Ph
OSiMe2Ph
n-C10H21
2x
+ Ph
OSiMe3
n-C10H21
2a
1i (1 eq.)
39%, 92 : 8 39%, 95 : 5
(24)
n-C10H21 SiMe2CH2DPh
O
H
Ph
OSiMe2CH2D
n-C10H21
+
+ Ph
OSiMe3
n-C10H21
1a-D' (1 eq.)
2a-D' 2a
+ n-Bu SiMe3
as above
+ Ph
OSiMe3
n-Bu
2z
+ Ph
OSiMe2CH2D
n-Bu
2z-D'
1k (1 eq.)
43%, 92 : 8 39%, 93 : 7
(25)
Scheme 4. A Revised Mechanism
R1 Si R2
SiO PtX2
R1 H
PtX2 R2CHO
R1PtX2
Si = SiR3
X = Cl, I
6'1
7PtX2
R2
OSi
R1
Si
2ッ
モ り
Grignard モ々 (Eq. 26)
り
㈻ ┘
11 1a1.3- (Eq. 27) 2
り 0
24
PhBr
Mg (4.0 eq.)
THF
r.t., 30 min
ZnCl2 (2.0 eq.)
THF / Et2O
r.t., 1.5 h
PtCl2 (10 mol%)
LiI (20 mol%)
PhCHO (1.0 eq.)
(CH2Cl)2
–30 °C to r.t., 1 h
Complex mixture. Ph
OH
Ph10a (4.0 eq.)
(26)
Not Observed
Ph
O
H
PtCl2 (10 mol%)
(CH2Cl)270 °C, 24 h
+PhSnBu3
PhPh
11 (1.0 eq.)
(27)
none :
LiI (20 mol%) :
1a, LiI (20 mol%) :
trace
trace
trace
0├ 10b
┘
(Eq. 28) [(PhCH=CH-)Pt(PPh3)2I]
モ
┘ り
0 (dba) 10b 1,3- (Eq. 29) dba
PhI
Pt(PPh3)4 (1.0 eq.) PhCHO (2.0 eq.)
No reaction. Ph
OR
Ph
Not Observed
Ph
OR
Ph
Not Observed
PhPh
(28)
(29)
10b
PhMe or (CH2Cl)2r.t. ~ 100 °C
Pt(dba)2 (1.0 eq.) PhCHO (2.0 eq.)10b
ConditionLiI (2-6 eq.)
Me3SiI (2 eq.)Additive
り 12 (Scheme 5) 12
2
25
Scheme 5. Hydrosilylation
R SiH+
PtX2 Pt Si
R
H Si
R
12
Ph
OSi
R
PhCHO
2
1- り
70 Υ 2y (Eq. 30) 2y
2y13i
(Eq. 31) 14)
n-C10H21
Ph
O
H
Et3SiH Ph
OSiEt3
n-C10H21
n-C10H21
SiEt3+ +PtCl2 (10mol%)
(CH2Cl)2, 24 h(2.0 eq.) (2.0 eq.)
+ (30)
2y
5%
0%
70 °C
r.t.
(E)-1i
<72%
80%
n-C10H21
Ph
O
H
Et3SiH+ +
PtCl2 (10mol%)
LiI (20 mol%)
(CH2Cl)2
70 , 24 h(2.0 eq.) (2.0 eq.)
n-C10H21 SiEt3
13i, 52%
(31)
ッ
Scheme 415) 0 り 6)
0 り
り 22 4 り
り
ぜ
さ
26
Ⅴ
Glass Tube Oven GTO-250 RS Ⅴ (bath temp.) (IR) FT/IR-230 ゝ
(1H NMR, 13C NMR) JEOL JNM-EX270 (1H NMR, 0.00 ppm) (1H NMR (CHCl3), 7.26 ppm), (13C NMR, 77.0 ppm ( )) (1H NMR (C6HD5), 7.16 ppm; 13C NMR, 128.0 ppm (
)) ㈻ QP-5050GC-17A ( DB-1 30.0 m 0.25 µl
0.25 mmID 100 kPa 32.5 cm / sec 15 1.40 mL / min2.5 mL / min N2)
モ
(THF) (Et2O) (DME)
⇩ (CH2Cl2) (DCE) (AcOEt)
⇩
モ
❻
モ
モ オ
(Z)-1- (1a): [70875-37-8]16)
n-C10H21 SiMe3 1- (10.1 g, 60.7 mmol) THF (130 mL) 0 Υ
n- (1.62 M in hexanes, 41.2 mL, 66.8 mmol) 0 Υ 2 (8.54 mL, 66.8 mmol) 0 Υ
↓ 18 (50 mL 2) ⇩
1- -1- (13a, 13.8 g, 57.9 mmol) 95% Bp 83–86 °C (0.50 Torr). 1H NMR (CDCl3) δ 0.15 (s, 9H), 0.88 (t, J = 6.4 Hz,
27
3H), 1.26–1.56 (m, 16H), 2.21 (t, J = 6.9 Hz, 2H). 13a (13.8 g, 57.9 mmol) Et2O (120 mL) 0 Υ
DIBAL-H (0.94 M in n-hexane, 68 mL, 64 mmol) ↓
36 0 Υ 20 w%2 M (50 mL
2) ⇩
(Z)-1- -1- (1a, 13.1 g, 54.5 mmol) 94%Bp 68–72 °C (0.45 Torr). 1H NMR (CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.9 Hz, 3H), 1.26–1.36 (m, 16H), 2.11 (q, J = 6.9 Hz, 2H), 5.46 (d, J = 14.0 Hz, 1H), 6.30 (dt, J = 14.0, 6.9 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3
3), 14.1 (CH3), 22.7 (CH2), 29.4 (CH2 2), 29.59 (CH2), 29.62 (CH2 2), 29.8 (CH2), 31.9 (CH2), 33.6 (CH2), 128.7 (CH), 149.4 (CH); MS m/z (relative intensity) 240 (M+, 0.63), 225 (M+ – Me, 27), 73 (100). (E)- -1- ((E)-1a): [70875-31-9]16)
n-C10H21
SiMe3
(E)-1a 1a 17) (4.0 mL) 1a (1.20 g, 5.00 mmol) Bu3SnH (146 mg) Et3B (1.01 M in n-hexane, 495 µL, 0.50 mmol) 60 Υ 24
DBU(E)- -1- ((E)-1a) 82% (E:Z = 97:3) 1H NMR
(CDCl3) δ 0.04 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.26–1.41 (m, 16H), 2.09 (q, J = 6.4 Hz, 2H), 5.61 (dt, J = 18.6, 1.5 Hz, 1H), 6.02 (dt, J = 18.6, 6.4 Hz, 1H); 13C NMR (CDCl3) δ –1.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 28.7 (CH2), 29.2 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 36.8 (CH2), 129.5 (CH), 147.5 (CH); MS m/z (relative intensity) 240 (M+, 1.8), 225 (M+ – Me, 48), 73 (100). (Z)-1- (1b): [4964-02-7]18)
Me SiMe3 1b (Z)-1- 18) (4.0 g,
0.58 mol) Et2O (100 mL) -28 Υ (Z)-1- (10.0 g, 82.7 mmol) Et2O (50 mL) 18
0 Υ (10.6 mL, 82.7 mmol) Et2O (50 mL) 0 Υ ↓ 22
(100mL 2) ⇩
(Z)-1- (1b, 4.09 g, 91 w%) 39% 1b Bp 88–90 °C. 1H NMR (CDCl3) δ 0.12 (s, 9H), 1.78 (dd,
J = 7.0, 1.6 Hz, 3H), 5.50 (dq, J = 14.0, 1.6 Hz, 1H), 6.39 (dq, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 19.0 (CH3), 130.0 (CH), 143.1 (CH); MS m/z (relative intensity) 114 (M+, 12), 99 (M+ – Me, 100), 73 (68). (Z)-2- -1- ( ) (1d): [66270-75-5]19)
28
SiMe3
1d 20)
(17.3 g, 66.0 mmol) (80 mL) (2.24 g, 20.0 mmol) 0 Υ
(10 mL) (14.6 g, 44.0 mmol) 101.5 (600 mL)
60 Υ/0.5 Torr 1,1- -2- 14, 4.69 g, 17.5 mmol88% Bp 60 °C (bath temp., 0.50 Torr). 1H NMR (CDCl3) δ 1.04–1.37 (m, 6H), 1.63–1.75 (m, 4H),
2.21–2.35 (m, 1H), 6.23 (d, J = 9.1 Hz, 1H). 13 (4.69 g, 17.5 mmol) THF (35 mL) -78 Υ
(1.67 M in hexanes, 21.3 mL, 35.0 mmol) 78 Υ 1↓ 15 (20 mL 3)
1- -2- (13d, 2.55 g, 14.1 mmol) 81% Bp 80-85 °C (8.5 Torr). 1H NMR (CDCl3) δ 0.14 (s, 9H), 1.24–1.79 (m, 10H), 2.33–2.42 (m, 1H).
13d 1d 13a 1a 1H NMR (CDCl3) δ 0.11 (s, 9H), 1.01–1.74 (m, 10H), 2.08–2.21 (m, 1H), 5.36 (d, J = 14.0 Hz, 1H), 6.11 (dd, J = 14.0, 10.0 Hz, 1H); 13C NMR (CDCl3) δ 0.4 (CH3 3), 25.8 (CH2 2), 25.9 (CH2), 33.1 (CH2 2), 42.7 (CH), 126.6 (CH), 155.0 (CH); MS m/z (relative intensity) 182 (M+, 5.6), 167 (M+ – Me, 10), 73 (100). (Z)-1- -2-( ) (1e): [19319-11-0]21)
Ph SiMe3 1e 1a 1H NMR (CDCl3) δ 0.05
(s, 9H), 5.83 (d, J = 15.2 Hz, 1H), 7.21–7.32 (m, 5H), 7.37 (d, J = 15.2 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 127.3 (CH), 127.9 (CH 2), 128.1 (CH 2), 132.8 (CH), 140.1 (C), 146.6 (CH); MS m/z (relative intensity) 176(M+, 27), 161 (M+ – Me, 100), 73 (15). (Z)-1- (4- )-2-( ) (1f): [119327-32-1]19)
Me3Si
MeO
1f (4- ) 1a 1H NMR
(C6D6) δ 0.16 (s, 9H), 3.27 (s, 3H), 5.80 (d, J = 15.0 Hz, 1H), 6.74 (dt, J = 8.7, 2.6 Hz, 2H), 7.24 (dt, J = 8.7, 2.6 Hz, 2H), 7.38 (d, J = 15.0 Hz, 1H); 13C NMR (C6D6) δ 0.4 (CH3 3), 54.7 (CH3), 113.7 (CH 2), 129.8 (CH 2), 130.6 (CH), 133.0 (C), 146.9 (CH), 159.7 (C); MS m/z (relative intensity) 206 (M+, 42), 191 (M+ – Me, 100). (Z)-1- (4- )-2-( ) (1g)
Me3Si
F3C
29
1g (4- ) 1a IR (neat) 1325, 1250, 1128 cm–1; 1H NMR (CDCl3) δ 0.05 (s, 9H), 5.97 (d, J = 15.3 Hz, 1H), 7.29 (d, J = 15.3 Hz, 1H), 7.37 (d, J = 8.2 Hz, 1H), 7.57 (d, J = 8.2 Hz, 1H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 124.2 (C, 1J(13C-19F) = 272.4 Hz), 124.9 (CH 2, 3J(13C-19F) = 3.4 Hz), 128.3 (CH), 129.3 (C, 2J(13C-19F) = 32.5 Hz), 135.5 (CH), 143.7 (C), 144.9 (CH); MS m/z (relative intensity) 244 (M+, 16), 229 (M+ – Me, 100), 73 (27). Anal. Calcd for C12H15F3Si: C, 58.99; H, 6.19. Found: C, 58.72; H, 6.27. (Z)- 1-tert- -1- (1h): [183290-32-6]22)
n-C10H21 SiMe2tBu
1h 1a 1H NMR (CDCl3) δ 0.08 (s, 6H), 0.88 (br s, 12H), 1.25–1.40 (m, 16H), 2.10 (q, J = 6.9 Hz, 2H), 5.45 (dt, J = 14.2, 1.3 Hz, 1H), 6.37 (dt, J = 14.2, 6.9 Hz, 1H); 13C NMR (CDCl3) δ –4.1 (CH3 2), 14.1 (CH3), 16.8 (C), 22.7 (CH2), 26.4 (CH3 3), 29.36 (CH2), 29.43 (CH2), 29.6 (CH2 3), 29.9 (CH2), 31.9 (CH2), 33.7 (CH2), 125.7 (CH), 150.3 (CH); MS m/z (relative intensity) 225 (M+ – tBu, 38), 99 (22), 73 (46), 59 (100). (Z)-1- -1- (1i): [108025-31-6]23)
n-C10H21 SiMe2Ph 1i 1a 1H NMR (CDCl3) δ 0.37 (s, 6H), 0.88 (t, J = 6.9 Hz, 3H), 1.19–1.35
(m, 16H), 2.03 (q, J = 7.0 Hz, 2H), 5.61 (br d, J = 14.0 Hz, 1H), 6.43 (dt, J = 14.0, 7.0 Hz, 1H), 7.33–7.35 (m, 3H), 7.54–7.56 (m, 2H); 13C NMR (CDCl3) δ –0.8 (CH3 2), 14.1 (CH3), 22.7 (CH2), 29.3 (CH2), 29.3 (CH2), 29.5 (CH2 2), 29.6 (CH2 2), 31.9 (CH2), 33.8 (CH2), 126.4 (CH), 127.7 (CH 2), 128.7 (CH), 133.7 (CH
2), 139.8 (C), 151.1 (CH); MS m/z (relative intensity) 302 (M+, 2.7), 287 (M+ – Me, 27), 135 (Me2PhSi+, 92), 121 (100). (Z)-1- -1- (1j): [52835-06-0]19)
n-Bu SiMe3 1j 1a 1H NMR (C6D6) δ 0.18 (s, 9H), 0.86 (t, J = 7.1 Hz, 3H), 1.23–1.33
(m, 4H), 2.12 (q, J = 7.0 Hz, 2H), 5.62 (d, J = 14.0 Hz, 1H), 6.34 (dt, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 14.0 (CH3), 22.4 (CH2), 32.0 (CH2), 33.3 (CH2), 128.7 (CH), 149.3 (CH); MS m/z (relative intensity) 156 (M+, 0.16), 141 (M+ – Me, 81), 73 (Me3Si+, 76), 59 (100). (Z)-2- -1- -1- (1a-D)
n-C10H21 SiMe3
D
1a-D 1- -1- (13a) 24)
13a (1.19 g, 5.00 mmol) Et2O (60 mL) (1.85 mL, 6.85 mmol) 78 Υ (0.95 M in Et2O, 13.2 mL, 12.5 mmol)
2 50 Υsec- (1.00 M in Et2O, 5.50 mL, 5.50 mmol) 50 Υ 1 (35 w% in D2O, 0.1 mL) (1 mL) 1
1 M (50 mL) (50 mL 3)
30
⇩
(Z)-2- -1--1- (1a-D, 0.759 g, 3.15 mmol) 63% ( : 92%D, α : 3%D) 1H NMR
(CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.5 Hz, 3H), 1.26–1.40 (m, 16H), 2.10 (t, J = 6.4 Hz, 2H), 5.45 (br s, 1H); 13C NMR (CDCl3) δ 0.2 (CH3 3), 14.1 (CH3), 22.7 (CH2), 29.34 (CH2), 29.37 (CH2), 29.58 (CH2), 29.61 (CH2 2), 29.75 (CH2), 31.9 (CH2), 33.4 (CH2), 128.5 (CH), 148.9 (CD, 2J(13C-D) = 23.0 Hz); MS m/z (relative intensity) 241 (M+, 0.44), 226 (M+ – Me), 73 (100). Anal. Calcd for 89% of C15H31DSi, 8% of C15H32Si and 3% of C15H30D2Si: C, 74.62; H, 13.75. Found: C, 74.46; H, 13.84. (Z)-1-[( ) ]-1- (1a-D´ �)
n-C10H21 SiMe2CH2D 1a-D �́ ( ) (PhMe2SiCH2Cl)
(0.271 g, 11.0 mmol) ⇩
10 Et2O (20 mL) PhMe2SiCH2Cl (1.85 g, 10.0 mmol) 2 0 Υ (1.81 g, 100 mmol) 10 1 N (30 mL) TBME (20 mL 3)
(40 mL) (40 mL) ⇩ (bath temp., 110 Υ
/ 45 Torr) ( ) (PhMe2SiCH2D, 1.26 g, 8.33 mmol) 83% (>99%D) 1H NMR (CDCl3) δ 0.24–0.28 (m, 8H), including 0.27 (s), 7.34–7.36 (m, 3H), 7.50–7.54 (m, 2H).
PhMe2SiCH2D (1.26 g, 8.33 mmol) (0.737 mL, 8.33 mmol) 11- (1.39 g, 8.33 mmol) THF (18 mL) 0 Υ
(1.66 M in hexanes, 5.02 mL, 8.33 mmol) 30Me2Si(OTf)CH2D 0 Υ
2 (30 mL) TBME (20 mL 3) (50 mL) ⇩
(bath temp., 90 Υ / 0.45 Torr) 1- 1-() -1- (13a-D �́, 1.79 g, 94 w%, 7.06 mmol) 85%
(>99%D) 1H NMR (CDCl3) δ 0.15 (s, 8H), 0.88 (t, J = 6.3 Hz, 3H), 1.27–1.51 (m, 16H), 2.21 (t, J = 7.0 Hz, 2H).
1a-D´ � 1a 13a-D �́ (94 w%) DIBAL-H 82% (>99%D) Bp 80 Υ (bath temp., 0.39 Torr). IR (neat) 2925, 2854, 1248, 839 cm-1; 1H NMR (C6D6) δ 0.17–0.21 (m, 8H), including 0.20 (s), 0.92 (t, J = 6.7 Hz, 3H), 1.29–1.41 (m, 16H), 2.17 (q, J = 7.0 Hz, 2H), 5.64 (d, J = 14.0 Hz, 1H), 6.39 (dt, J = 14.0, 7.0 Hz, 1H); 13C NMR (CDCl3) δ –0.1 (CD, 2J(13C-D) = 17.9 Hz), 0.2 (CH3 2), 14.1 (CH3), 22.7 (CH2), 29.35 (CH2), 29.37 (CH2), 29.59 (CH2), 29.61 (CH2 2), 29.8 (CH2), 31.9 (CH2), 33.6 (CH2), 128.7 (CH), 149.4 (CH); MS m/z (relative intensity) 241 (M+, 0.70), 226 (M+ – Me), 74 (Me2Si+CH2D, 100). Anal. Calcd for C15H31DSi: C, 74.60; H, 13.77. Found: C, 74.57; H, 13.94. (E)-1- -2- (10b): [42599-24-6]25)
PhI
(10.2 g, 10.0 mmol) (2.91 g,
31
10.0 mmol) AIBN (50 mg, 0.3 mmol) (20 mL) 90 Υ 24-78 Υ (3.8 g, 15.0 mmol) THF (10 mL)
30 (30 mL) (30 mL)
TBME (20 mL 3) ⇩
(E)-1- -2- (10b, 2.01 g, 0.87 mmol) 87% (E)-1- -2-( ) (11): [66680-88-4]26)
PhSnBu3
(10.2 g, 10.0 mmol) (2.91 g, 10.0 mmol) AIBN (50 mg, 0.3 mmol) (20 mL) 90 Υ 2
(156 Υ / 0.49 Torr) (E)-1--2-( ) (9, 3.69 g, 9.4 mmol) 94%
Schlenck (0.05 mmol) (0.10
mmol) 1,2- (1.5 mL) (0.50 mmol) (1.00
mmol) 70 Υ ス
り
┘ 2-[ ( ) ]-1- (2a)
Ph
OSiMe3
n-C10H21 Bp 180 °C (bath temp., 8.0 Torr). IR (neat) 1252, 1090, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88
(t, J = 6.4 Hz, 3H), 1.20–1.40 (m, 16H), 1.75 (dt, J = 15.5, 7.5 Hz, 1H), 1.92 (dt, J = 15.5, 7.5 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.14 (s, 1H), 7.22–7.34 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.36 (CH2), 29.46 (CH2), 29.52 (CH2), 29.61 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 346 (M+, 16), 73 (100). Anal. Calcd for C22H38OSi: C, 76.23; H, 11.05. Found: C, 76.13; H, 11.21. 2-[(1- )( ) ]-1- (2b)
OSiMe3
n-C10H21 Bp 170 °C (bath temp., 0.45 Torr). IR (neat) 1252, 1088, 891 cm–1; 1H NMR (CDCl3) δ 0.06 (s, 9H), 0.87
(t, J = 6.9 Hz, 3H), 1.23–1.35 (m, 16H), 1.83 (dt, J = 15.8, 7.9 Hz, 1H), 1.98 (dt, J = 15.8, 7.9 Hz, 1H), 4.96
32
(s, 1H), 5.13 (s, 1H), 5.76 (s, 1H), 7.42–7.48 (m, 3H), 7.63 (d, J = 6.8 Hz, 1H), 7.76 (d, J = 8.1 Hz, 1H), 7.82–7.86 (m, 1H), 8.13–8.17 (m, 1H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.9 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 32.0 (CH2), 75.6 (CH), 110.9 (CH2), 124.3 (CH), 125.19 (CH), 125.24 (CH 2), 125.4 (CH), 127.9 (CH), 128.6 (CH), 130.9 (C), 133.8 (C), 138.3 (C), 151.2 (C); MS m/z (relative intensity) 396 (M+, 23), 73 (100). Anal. Calcd for C26H40OSi: C, 78.72; H, 10.16. Found: C, 78.55; H, 10.35. 2-[(4- )( ) ]-1- (2c)
OSiMe3
n-C10H21O2N
Bp 180 °C (bath temp., 0.80 Torr). IR (neat) 1523, 1348, 1252, 1086 cm–1; 1H NMR (CDCl3) δ 0.12 (s, 9H), 0.87 (t, J = 6.4 Hz, 3H), 1.20–1.40 (m, 16H), 1.69 (dt, J = 16.5, 7.6 Hz, 1H), 1.92 (dt, J = 16.5, 7.6 Hz, 1H), 4.94 (s, 1H), 5.17 (s, 1H), 5.20 (s, 1H), 7.51 (d, J = 8.5 Hz, 2H), 8.16 (d, J = 8.5 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.6 (CH2), 27.6 (CH2), 29.3 (CH2), 29.4 (CH2), 29.4 (CH2), 29.5 (CH2 2), 30.1 (CH2), 31.9 (CH2), 77.7 (CH), 111.4 (CH2), 123.3 (CH 2), 127.0 (CH 2), 147.1 (C), 150.6 (C), 150.8 (C); MS m/z (relative intensity) 391 (M+, 1.1), 374 (M+ – Me, 7.7), 73 (100). Anal. Calcd for C22H37NO3Si: C, 67.47; H, 9.52; N 3.58. Found: C, 67.57; H, 9.63; N, 3.66. 4-(2- -1- -2- ) (2d)
OSiMe3
n-C10H21MeO2C
Bp 180 °C (bath temp., 0.50 Torr). IR (neat) 1728, 1277, 1109, 1084 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.32 (m, 16H), 1.72 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 3.90 (s, 3H), 4.90 (d, J = 1.5 Hz, 1H), 5.16 (s, 2H), 7.40 (d, J = 8.3 Hz, 2H), 7.97 (d, J = 8.3 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.31 (CH2), 29.39 (CH2), 29.45 (CH2), 29.56 (CH2 2), 30.5 (CH2), 31.9 (CH2), 52.0 (CH3), 77.9 (CH), 110.6 (CH2), 126.3 (CH 2), 128.8 (C), 129.3 (CH 2), 148.5 (C), 151.1 (C), 167.1 (C); MS m/z (relative intensity) 389 (M+ – Me, 4.0), 73 (100). Anal. Calcd for C24H40O3Si: C, 71.23; H, 9.96. Found: C, 71.27; H, 10.19. 2-[(4- )( ) ]-1- (2e)
OSiMe3
n-C10H21NC
Bp 170 °C (bath temp., 0.63 Torr). IR (neat) 2229, 1252, 1084 cm–1; 1H NMR (CDCl3) δ 0.11 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.20–1.30 (m, 16H), 1.68 (dt, J = 16.2, 8.1 Hz, 1H), 1.90 (dt, J = 16.2, 8.1 Hz, 1H), 4.92 (d, J = 1.2 Hz, 1H), 5.15 (s, 2H), 7.45 (d, J = 8.3 Hz, 2H), 7.60 (d, J = 8.3 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.31 (CH2), 29.37 (CH2), 29.44 (CH2), 29.55 (CH2 2), 30.2 (CH2), 31.9 (CH2), 77.8 (CH), 110.7 (C), 111.2 (CH2), 119.04 (C), 126.9 (CH 2), 131.9 (CH 2), 148.8 (C), 150.7 (C); MS m/z (relative intensity) 371 (M+, 3.5), 356 (M+ – Me, 2.8) 73 (100). Anal. Calcd for C23H37NOSi: C, 74.33; H, 10.04; N, 3.77. Found: C, 74.23; H, 10.12; N, 3.82.
33
2-[(4- )( ) ]-1- (2f)
OSiMe3
n-C10H21Ac
Bp 245 °C (bath temp., 1.3 Torr). IR (neat) 1687, 1606, 1265, 1084 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.36 (m, 16H), 1.72 (dt, J = 15.6, 7.8 Hz, 1H), 1.92 (dt, J = 15.6, 7.8 Hz, 1H), 2.59 (s, 3H), 4.91 (d, J = 1.5 Hz, 1H), 5.16 (s, 2H), 7.43 (d, J = 8.6 Hz, 2H), 7.90 (d, J = 8.6 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 26.6 (CH2), 27.7 (CH3), 29.31 (CH2), 29.40 (CH2), 29.46 (CH2), 29.56 (CH2 2), 30.5 (CH2), 31.9 (CH2), 77.8 (CH), 110.7 (CH2), 126.5 (CH 2), 128.2 (CH2), 136.0 (C), 148.8 (C), 151.1 (C), 197.9 (C); MS m/z (relative intensity) 388 (M+, 9.5), 73 (100). Anal. Calcd for C24H40O2Si: C, 74.17; H, 10.37. Found: C, 73.99; H, 10.39. 2-[(4- )( ) ]-1- (2g)
OSiMe3
n-C10H21F
Bp 143 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1223, 1080 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.37 (m, 16H), 1.73 (dt, J = 15.8, 7.9 Hz, 1H), 1.90 (dt, J = 15.8, 7.9 Hz, 1H), 4.89 (s, 1H), 5.08 (s, 1H), 5.14 (s, 1H), 6.98 (dd, J = 8.8, 8.8 Hz, 2H), 7.28 (dd, J = 8.8, 5.6 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.32 (CH2), 29.42 (CH2), 29.48 (CH2), 29.58 (CH2 2), 30.7 (CH2), 31.9 (CH2), 77.4 (CH), 110.0 (CH2), 114.7 (CH 2, 2J(13C-19F) = 21.3 Hz), 128.0 (CH
2, 3J(13C-19F) = 7.8 Hz), 138.9 (C, 4J(13C-19F) = 2.8 Hz), 151.5 (C), 161.9 (C, 1J(13C-19F) = 244.7 Hz); MS m/z (relative intensity) 364 (M+, 3.1), 349 (M+ – Me, 2.0), 73 (100). Anal. Calcd for C22H37FOSi: C, 72.47; H, 10.23. Found: C, 72.09; H, 10.29. 2-[(4- )( ) ]-1- (2h)
OSiMe3
n-C10H21Cl
Bp 180 °C (bath temp., 0.55 Torr). IR (neat) 1489, 1252, 1014 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.87 (t, J = 6.4 Hz, 3H), 1.19–1.33 (m, 16H), 1.72 (dt, J = 15.4, 7.4 Hz, 1H), 1.90 (dt, J = 15.4, 7.2 Hz, 1H), 4.88 (s, 1H), 5.08 (s, 1H), 5.20 (s, 1H), 7.26 (s, 4H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.12 (CH3), 22.7 (CH2), 27.7 (CH2), 29.36 (CH2), 29.43 (CH2), 29.51 (CH2), 29.60 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.5 (CH), 110.2 (CH2), 127.8 (CH 2), 128.1 (CH 2), 132.6 (C), 141.8 (C), 151.3 (C); MS m/z (relative intensity) 382 (M+ + 2, 1.7), 380 (M+, 1.6), 73 (100). Anal. Calcd for C22H37ClOSi: C, 69.34; H, 9.79. Found: C, 69.44; H, 9.87. 2-[(2- )( ) ]-1- (2i)
OSiMe3
n-C10H21
Cl
34
Bp 148 °C (bath temp., 0.56 Torr). IR (neat) 1468, 1441, 1252, 1084 cm–1; 1H NMR (CDCl3) δ 0.07 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.23–1.42 (m, 16H), 1.86 (dt, J = 15.0, 7.5 Hz, 1H), 1.97 (dt, J = 15.0, 7.5 Hz, 1H), 4.90 (s, 1H), 5.05 (s, 1H), 5.54 (s, 1H), 7.14–7.31 (m, 3H), 7.51 (dd, J = 7.6, 2.0 Hz, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.9 (CH2), 29.33 (CH2), 29.42 (CH2), 29.50 (CH2), 29.60 (CH2 2), 31.8 (CH2), 31.9 (CH2), 73.1 (CH), 110.5 (CH2), 126.7 (CH), 128.3 (CH), 129.0 (CH×2), 132.4 (C), 140.7 (C), 150.3 (C); MS m/z (relative intensity) 382 (M+ + 2, 1.6), 380 (M+, 4.2), 73 (100). Anal. Calcd for C22H37ClOSi: C, 69.34; H, 9.79. Found: C, 69.28; H, 9.94. 2-[(4- )( ) ]-1- (2j)
OSiMe3
n-C10H21Br
Bp 150 °C (bath temp., 0.51 Torr). IR (neat) 1252, 1072, 891, 841 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.6 Hz, 3H), 1.21–1.33 (m, 16H), 1.72 (dt, J = 15.8, 7.9 Hz, 1H), 1.90 (dt, J = 15.8, 7.9 Hz, 1H), 4.88 (d, J = 1.5 Hz, 1H), 5.06 (s, 1H), 5.12 (s, 1H), 7.20 (d, J = 8.5 Hz, 2H), 7.42 (d, J = 8.5 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.32 (CH2), 29.41 (CH2), 29.48 (CH2), 29.59 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.5 (CH), 110.3 (CH2), 127.8 (CH 2), 128.2 (CH 2), 131.0 (C), 142.3 (C), 151.3 (C); MS m/z (relative intensity) 426 (M+ + 2, 1.1), 424 (M+, 0.9), 73 (100). Anal. Calcd for C22H37BrOSi: C, 62.10; H, 8.76. Found: C, 62.26; H, 8.85. 2-[(4- )( ) ]-1- (2k)
OSiMe3
n-C10H21I
Bp 159 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1082, 1007 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.33 (m, 16H), 1.72 (dt, J = 16.4, 8.2 Hz, 1H), 1.90 (dt, J = 16.4, 8.2 Hz, 1H), 4.88 (s, 1H), 5.05 (s, 1H), 5.12 (s, 1H), 7.08 (d, J = 8.4 Hz, 2H), 7.62 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.5 (CH2), 31.9 (CH2), 77.6 (CH), 92.4 (C), 110.3 (CH2), 128.5 (CH 2), 137.0 (CH 2), 143.0 (C), 151.3 (C); MS m/z (relative intensity) 472 (M+, 1.7), 75 (100), 73 (39). Anal. Calcd for C22H37IOSi: C, 55.92; H, 7.89. Found: C, 55.94; H, 7.86. 2-[(4- )( ) ]-1- (2l)
OSiMe3
n-C10H21Me
Bp 165 °C (bath temp., 0.50 Torr). IR (neat) 1252, 1080, 895, 841 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.9 Hz, 3H), 1.21–1.38 (m, 16H), 1.75 (dt, J = 15.7, 7.4 Hz, 1H), 1.92 (dt, J = 15.7, 7.4 Hz, 1H), 2.32 (s, 3H), 4.87 (s, 1H), 5.07 (s, 1H), 5.14 (s, 1H), 7.10 (d, J = 8.1 Hz, 2H), 7.20 (d, J = 8.1 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 21.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.33 (CH2), 29.45 (CH2), 29.51 (CH2), 29.60 (CH2 2), 30.9 (CH2), 31.9 (CH2), 77.8 (CH), 109.5 (CH2), 126.4 (CH 2), 128.7 (CH2), 136.5 (C), 140.2 (C), 151.8 (C); MS m/z (relative intensity) 360 (M+, 3.0), 345 (M+ – Me, 16), 73 (100).
35
Anal. Calcd for C23H40OSi: C, 76.60; H, 11.18. Found: C, 76.44; H, 10.98. 2-[(4- )( ) ]-1- (2m)
OSiMe3
n-C10H21MeO
Bp 183 °C (bath temp., 0.79 Torr). IR (neat) 1510, 1250, 1080, 895, 841 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 0.88 (t, J = 6.5 Hz, 3H), 1.22–1.38 (m, 16H), 1.76 (dt, J = 15.0, 7.5 Hz, 1H), 1.91 (dt, J = 15.0, 7.5 Hz, 1H), 3.80 (s, 3H), 4.87 (s, 1H), 5.06 (s, 1H), 5.14 (s, 1H), 6.83 (d, J = 8.6 Hz, 2H), 7.23 (d, J = 8.6 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.33 (CH2), 29.46 (CH2), 29.51 (CH2), 29.59 (CH2 2), 31.0 (CH2), 31.9 (CH2), 55.2 (CH3), 77.4 (CH), 109.4 (CH2), 113.3 (CH 2), 127.7 (CH 2), 135.3 (C), 151.9 (C), 158.6 (C); MS m/z (relative intensity) 376 (M+, 0.52), 361 (M+ – Me, 0.41), 159 (100). Anal. Calcd for C23H40O2Si: C, 73.34; H, 10.70. Found: C, 73.01; H, 10.70. 2-[(4- )( ) ]-1- (2n)
OSiMe3
n-C10H21AcO
Bp 208 °C (bath temp., 0.48 Torr). IR (neat) 1768, 1200 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.1 Hz, 3H), 1.22–1.38 (m, 16H), 1.74 (dt, J = 15.4, 7.7 Hz, 1H), 1.92 (dt, J = 15.4, 7.7 Hz, 1H), 2.29 (s, 3H), 4.88 (s, 1H), 5.11 (s, 1H), 5.14 (s, 1H), 7.02 (d, J = 8.7 Hz, 2H), 7.33 (d, J = 8.7 Hz, 2H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 21.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.6 (CH2), 31.9 (CH2), 77.6 (CH), 110.0 (CH2), 120.9 (CH 2), 127.4 (CH 2), 140.7 (C), 149.6 (C), 151.5 (C), 169.4 (C); MS m/z (relative intensity) 404 (M+, 1.5), 389 (M+ – Me, 3.5), 345 (M+ – AcO, 30) 73 (100). Anal. Calcd for C22H44OSi: C, 71.23; H, 9.96. Found: C, 71.22; H, 10.10. 2-[2- -1-( ) ]-1- (2o)
OSiMe3
n-C10H21 Bp 190 Υ (bath temp., 0.50 Torr). IR (neat) 1250, 1068, 887, 841 cm-1; 1H NMR (CDCl3) δ 0.07 (s, 9H),
0.80-0.90 (m, 9H), 1.18–1.55 (m, 21H), 1.75 (dt, J = 16.9, 7.9 Hz, 1H), 1.92 (dt, J = 16.9, 7.9 Hz, 1H), 3.93 (d, J = 5.9 Hz, 1H), 4.83 (d, J = 1.6 Hz, 1H), 4.92 (s, 1H); 13C NMR (CDCl3) δ 0.19 (CH3 3), 10.91 (CH3), 11.07 (CH3), 14.12 (CH3), 20.18 (CH2), 21.52 (CH3), 22.69 (CH2), 27.78 (CH2), 29.35 (CH2), 29.60 (CH2), 29.65 (CH2 2), 29.70 (CH2), 30.50 (CH2), 31.91 (CH2), 43.63 (CH), 78.29 (CH), 110.18 (CH2), 150.95 (C); MS m/z (relative intensity) 340 (M+, 1), 269 (31), 143 (76), 73 (100). Anal. Calcd for C21H44OSi: C, 74.04; H, 13.02. Found: C, 74.05; H, 13.14. 2-[ ( ) ]-1- (2p)
OSiMe3
n-C10H21 Bp 175 °C (bath temp., 0.35 Torr). IR (neat) 2360, 1250, 1063, 841 cm–1; 1H NMR (CDCl3) δ 0.07 (s, 9H),
36
0.77–0.90 (m, 5H) including 0.88 (t, J = 6.3 Hz), 1.07–1.92 (m, 26H), 2.05 (dt, J = 16.0, 7.9 Hz, 1H), 3.67 (d, J = 7.6 Hz, 1H), 4.79 (d, J = 1.6 Hz, 1H), 4.84 (s, 1H); 13C NMR (CDCl3) δ –0.2 (CH3 3), 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 26.3 (CH2), 26.6 (CH2), 27.8 (CH2), 29.0 (CH2), 29.3 (CH2), 29.62 (CH2), 29.65 (CH2 2), 29.72 (CH2), 29.88 (CH2 2), 31.9 (CH2), 41.0 (CH), 82.3 (CH), 110.3 (CH2), 150.6 (C); MS m/z (relative intensity) 352 (M+, 5), 269 (M+ – C6H11, 31), 143 (100), 73 (99). Anal. Calcd for C22H44OSi: C, 74.92; H, 12.58. Found: C, 74.86; H, 12.62. 2- -4- -3-( )-1,4- (2q)
OSiMe3
n-C10H21 Bp 118 °C (bath temp., 10 Torr). IR (neat) 1252, 1090, 901, 841 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H),
0.88 (t, J = 6.8 Hz, 3H), 1.26–1.46 (m, 16H), 1.59 (s, 3H), 1.78–2.00 (m, 2H), 4.43 (s, 1H), 4.86 (s, 2H), 4.99 (t, J = 1.1 Hz, 1H), 5.08 (s, 1H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.1 (CH3), 17.6 (CH3), 22.7 (CH2), 27.9 (CH2), 29.35 (CH2), 29.58 (CH2 2), 29.64 (CH2 2), 31.1 (CH2), 31.9 (CH2), 79.4 (CH), 109.8 (CH2), 111.6 (CH2), 145.9 (C) 149.6 (C); MS m/z (relative intensity) 310 (M+, 1.5), 295 (M+ – Me, 5.3), 73 (100). Anal. Calcd for C19H38OSi: C, 73.47; H, 12.33. Found: C, 73.18; H, 12.19. 2- -3- -3-( ) (2r) : [83205-05-4]
Ph
OSiMe3
Me Bp 75 °C (bath temp., 1.3 Torr). IR (neat) 2958, 1252, 1092, 1066 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H),
1.55 (s, 3H), 4.87 (t, J = 1.5 Hz, 1H), 5.10 (br s, 2H), 7.20–7.36 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 17.4 (CH3), 78.3 (CH), 111.2 (CH2), 126.2 (CH 2), 126.9 (CH), 128.0 (CH 2), 142.9 (C), 147.6 (C); MS m/z (relative intensity) 220 (M+, 8.7), 205 (M+ – Me, 25), 73 (100). Anal. Calcd for C13H20OSi: C, 70.85; H, 9.15. Found: C, 71.02; H, 8.87. 2- -3- -3-( ) (2r �́)
OSiMe3
MeCl
Bp 90 °C (bath temp., 1.3 Torr). IR (neat) 1491, 1252, 1086, 891 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 1.52 (s, 3H), 4.87 (t, J = 1.5 Hz, 1H), 5.07 (s, 2H), 7.27 (s, 4H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 17.2 (CH3), 77.7 (CH), 111.7 (CH2), 127.6 (CH 2), 128.1 (CH 2), 132.6 (C), 141.6 (C), 147.2 (C); MS m/z (relative intensity) 256 (M++2, 1.9), 254 (M+, 6.2), 73 (100). Anal. Calcd for C13H19ClOSi: C, 61.27; H, 7.52. Found: C, 61.34; H, 7.53. 2- -3- -3-( ) (2s)
Ph
OSiMe3
37
Bp 110 °C (bath temp., 0.9 Torr). IR (neat) 2925, 2852, 1252 cm–1; 1H NMR (CDCl3) δ 0.08 (s, 9H), 1.01–1.26 (m, 5H), 1.54–1.80 (m, 6H), 4.93 (s, 1H), 5.13 (s, 1H), 5.15 (t, J = 1.5 Hz, 1H), 7.20–7.33 (m, 5H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 26.3 (CH2), 26.8 (CH2), 26.9 (CH2), 33.3 (CH2), 34.2 (CH2), 39.7 (CH), 77.2 (CH), 108.6 (CH2), 126.9 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 157.1 (C); MS m/z (relative intensity) 288 (M+, 16), 205 (M+ – C6H11, 52), 73 (100). Anal. Calcd for C18H28OSi: C, 74.94; H, 9.78. Found: C, 74.90; H, 9.68. 2,3- -3-( ) (2t)
Ph
OSiMe3
Ph Bp 120 °C (bath temp., 1.3 Torr). IR (neat) 1252, 1066, 698 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 5.41 (s,
1H), 5.48 (s, 1H), 5.60 (s, 1H), 7.15–7.34 (m, 10H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.8 (CH), 114.0 (CH2), 126.8 (CH 2), 127.1 (CH), 127.2 (CH), 127.3 (CH 2), 127.9 (CH 2), 128.1 (CH 2), 139.7 (C), 142.7 (C), 150.9 (C); MS m/z (relative intensity) 282 (M+, 2.6), 267 (M+ – Me, 1.5), 73 (100). Anal. Calcd for C18H22OSi: C, 76.54; H, 7.85. Found: C, 76.71; H, 7.74. 3- -3-[4-( ) ]-3-( ) (2u)
F3C
Ph
Me3SiO
Bp 106 °C (bath temp., 0.82 Torr). IR (neat) 1327, 1254, 1068 cm–1; 1H NMR (CDCl3) δ 0.10 (s, 9H), 5.46
(s, 1H), 5.56 (s, 1H), 5.59 (s, 1H), 7.20–7.32 (m, 5H), 7.36 (d, J = 8.4 Hz, 2H), 7.45 (d, J = 8.4 Hz, 2H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.9 (CH), 115.8 (CH2), 124.2 (C, 1J(13C-19F) = 271.9 Hz) 124.8 (CH 2, 3J(13C-19F) = 3.9 Hz), 126.6 (CH 2), 127.3 (CH), 127.7 (CH 2), 128.2 (CH 2), 129.2 (C, 2J(13C-19F) = 32.5 Hz), 142.1 (C), 143.1 (C), 149.9 (C); MS m/z (relative intensity) 350 (M+, 1.2), 335 (M+ – Me, 4.5), 179 (100), 73 (64). Anal. Calcd for C19H21F3OSi: C, 65.12; H, 6.04. Found: C, 64.86; H, 6.11. 2-[(t- )( ) ]-1- (2v)
Ph
OSiMe2t-Bu
n-C10H21 Bp 180 °C (bath temp., 0.8 Torr). IR (neat) 1254, 1092, 1066 cm–1; 1H NMR (CDCl3) δ 0.04 (s, 3H), 0.05
(s, 3H), 0.91 (s, 12H) including 0.88 (t, J = 6.9 Hz), 1.14–1.32 (m, 16H), 1.73 (dt, J = 15.8, 8.0 Hz, 1H), 1.91 (dt, J = 15.8, 8.0 Hz, 1H), 4.84 (s, 1H), 5.11 (s, 1H), 5.17 (s, 1H), 7.23–7.34 (m, 5H); 13C NMR (CDCl3) δ –5.0 (CH3), –4.9 (CH3), 14.1 (CH3), 18.3 (C), 22.7 (CH2), 25.8 (CH3 3), 27.7 (CH2), 29.32 (CH2), 29.45 (CH2), 29.49 (CH2), 29.57 (CH2 2), 30.4 (CH2), 31.9 (CH2), 78.4 (CH), 109.4 (CH2), 126.3 (CH 2), 126.8 (CH), 127.9 (CH 2), 143.5 (C), 152.0 (C); MS m/z (relative intensity) 331 (M+ – C4H9, 61), 75 (100). Anal. Calcd for C25H44OSi: C, 77.25; H, 11.41. Found: C, 77.16; H, 11.20. 2-[( )( ) ]-1- (2w)
Ph
OSiMe2Ph
n-C10H21 Bp 188 °C (bath temp., 0.43 Torr). IR (neat) 1252, 1088, 1065, 698 cm–1; 1H NMR (CDCl3) d 0.31 (s, 3H),
38
0.35 (s, 3H), 0.88 (t, J = 6.4 Hz, 3H), 1.15–1.35 (m, 16H), 1.72 (dt, J = 15.5, 7.5 Hz, 1H), 1.90 (dt, J = 15.5, 7.5 Hz, 1H), 4.87 (s, 1H), 5.11 (s, 1H), 5.16 (s, 1H), 7.19–7.31 (m, 5H), 7.33–7.37 (m, 3H), 7.53–7.56 (m, 2H); 13C NMR (CDCl3) d –1.16 (CH3), –1.13 (CH3), 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.32 (CH2), 29.40 (CH2), 29.48 (CH2), 29.59 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.3 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.7 (CH 2), 127.9 (CH 2), 129.5 (CH), 133.6 (CH 2), 137.9 (C), 142.9 (C), 151.4 (C); MS m/z (relative intensity) 408 (M+, 10), 135 (100). Anal. Calcd for C27H40OSi: C, 79.35; H, 9.87. Found: C, 79.04; H, 9.77. 2-[ ( ) ]-1- (2y)
Ph
OSiMe3
n-Bu Bp 79 °C (bath temp., 0.38 Torr). IR (neat) 1252, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.83 (t, J =
7.2 Hz, 3H), 1.17–1.40 (m, 4H), 1.76 (dt, J = 15.4, 7.7 Hz, 1H), 1.94 (dt, J = 15.4, 7.7 Hz, 1H), 4.89 (d, J = 1.6 Hz, 1H), 5.12 (s, 1H), 5.15 (q, J = 0.8 Hz, 1H), 7.20–7.35 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3 3), 14.0 (CH3), 22.5 (CH2), 29.9 (CH2), 30.5 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 126.9 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 262 (M+, 18), 73 (100). Anal. Calcd for C16H26OSi: C, 73.22; H, 9.98. Found: C, 72.97; H, 10.23. 2-[ ( ) ]-1- (2z)
Ph
OSiEt3
n-C10H21 Bp 203 °C (bath temp., 0.61 Torr). IR (neat) 1458, 1090 cm–1; 1H NMR (CDCl3) δ 0.58 (q, J = 8.3 Hz, 9H),
0.85–0.93 (m, 12H), 1.14–1.36 (m, 16H), 1.73 (dt, J = 16.1, 8.1 Hz, 1H), 1.92 (dt, J = 16.1, 8.1 Hz, 1H), 4.85 (s, 1H), 5.12 (s, 1H), 5.19 (s, 1H), 7.20–7.36 (m, 5H); 13C NMR (CDCl3) δ 4.8 (CH2 3), 6.8 (CH3 3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.5 (CH2), 31.9 (CH2), 78.0 (CH), 109.3 (CH2), 126.3 (CH 2), 126.9 (CH), 127.9 (CH 2), 143.5 (C), 152.0 (C); MS m/z (relative intensity) 388 (M+, 6.7), 359 (M+ – Et, 29), 129 (100), 103 (21). Anal. Calcd for C25H44OSi: C, 77.25; H, 11.41. Found: C, 77.29; H, 11.28. 1- -2-[ ( ) ]-1- (2a-D)
Ph
OSiMe3
n-C10H21
D
1a-D (1.00 mmol) (0.50 mmol)
2a-D 87% (86%D) Bp 128 °C (bath temp., 0.46 Torr). IR (neat) 1252, 1090, 1066 cm–1; 1H NMR (CDCl3) δ 0.09 (s, 9H), 0.88 (t, J = 6.4 Hz, 3H), 1.21–1.34 (m, 16H), 1.75 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 4.87 (s, 0.41H), 5.11 (s,1H), 5.13 (s, 0.70H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ 0.0 (CH3), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.5 (CD, 2J(13C-D) = 24.6 Hz), 126.5 (CH 2), 127.0 (CH), 127.9 (CH
2), 143.1 (C), 151.6 (C); MS m/z (relative intensity) 347 (M+, 5.5), 73 (100). Anal. Calcd for 83% of C22H37DOSi, 14% of C22H38OSi and C22H36D2OSi: C, 76.04; H, 11.28. Found: C, 75.91; H, 11.44. 2-[( ) ] ]-1- (2a-D’)
39
Ph
OSiMe2CH2D
n-C10H21 Bp 125 °C (bath temp., 0.53 Torr). IR (neat) 1252, 1090, 1067 cm–1; 1H NMR (CDCl3) δ 0.06–0.09 (m,
8H) including 0.09 (s), 0.87 (t, J = 6.6 Hz, 3H), 1.21–1.36 (m, 16H), 1.75 (dt, J = 15.8, 7.9 Hz, 1H), 1.92 (dt, J = 15.8, 7.9 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.15 (s, 1H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ –0.2 (CD, 2J(C-D) = 17.9 Hz), 0.0 (CH3 2), 14.1 (CH3), 22.7 (CH2), 27.7 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2 2), 30.8 (CH2), 31.9 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 347 (M+, 20), 74 (100). Anal. Calcd for C22H37DOSi: C, 76.01; H, 11.31. Found: C, 76.04; H, 11.40. 2-[( ) ] ]-1- (2y-D’)
Ph
OSiMe2CH2D
n-Bu Bp 85 °C (bath temp., 0.75 Torr). IR (neat) 1252, 1066 cm–1; 1H NMR (CDCl3) δ 0.06–0.11 (m, 8H)
including 0.09 (s), 0.83 (t, J = 7.1 Hz, 3H), 1.17–1.40 (m, 4H), 1.76 (dt, J = 15.6, 7.8 Hz, 1H), 1.94 (dt, J = 15.6, 7.8 Hz, 1H), 4.88 (s, 1H), 5.11 (s, 1H), 5.15 (q, J = 0.8 Hz, 1H), 7.20–7.34 (m, 5H); 13C NMR (CDCl3) δ –0.3 (CD, 2J(C-D) = 17.9 Hz), 0.0 (CH3 2), 14.0 (CH3), 22.5 (CH2), 29.9 (CH2), 30.5 (CH2), 78.0 (CH), 109.8 (CH2), 126.5 (CH 2), 127.0 (CH), 127.9 (CH 2), 143.1 (C), 151.7 (C); MS m/z (relative intensity) 263 (M+, 18), 74 (100). Anal. Calcd for C16H25DOSi: C, 72.94; H, 10.33. Found: C, 72.67; H, 10.41. 2-( )-1- (3a)
Ph
OMe
n-C10H21 Bp 175 °C (bath temp., 0.57 Torr). IR (neat) 1452, 1097 cm–1; 1H NMR (CDCl3) δ 0.88 (t, J = 6.8 Hz, 3H),
1.22–1.40 (m, 16H), 1.80 (dt, J = 16.2, 8.1 Hz, 1H), 1.91 (dt, J = 16.2, 8.1 Hz, 1H), 3.32 (s, 3H), 4.59 (s, 1H), 4.98 (d, J = 1.5 Hz, 1H), 5.17 (s, 1H), 7.22–7.33 (m, 5H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.6 (CH2), 29.32 (CH2), 29.42 (CH2), 29.48 (CH2), 29.58 (CH2 2), 31.1 (CH2), 31.9 (CH2) 56.6 (CH3), 86.8 (CH), 111.0 (CH2), 126.8 (CH 2), 127.4 (CH), 128.1 (CH 2), 140.6 (C), 149.1 (C); MS m/z (relative intensity) 288 (M+, 14), 147 (66), 121 (100). Anal. Calcd for C20H32O: C, 83.27; H, 11.18. Found: C, 83.12; H, 11.36. 2-[ (4- ) ]-1- (3b)
OMe
n-C10H21Cl
Bp 178 °C (bath temp., 0.67 Torr). IR (neat) 1491, 1466, 1092 cm–1; 1H NMR (CDCl3) δ 0.88 (t, J = 6.9 Hz, 3H), 1.21–1.41 (m, 16H), 1.75 (dt, J = 15.6, 7.8 Hz, 1H), 1.88 (dt, J = 15.6, 7.8 Hz, 1H), 3.31 (s, 3H), 4.56 (s, 1H), 4.99 (d, J = 1.5 Hz, 1H), 5.15 (s, 1H), 7.27 (s, 4H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.5 (CH2), 29.32 (CH2), 29.41 (CH2), 29.47 (CH2), 29.59 (CH2 2), 30.8 (CH2), 31.9 (CH2) 56.6 (CH3), 86.2 (CH), 111.7 (CH2), 128.1 (CH 2), 128.3 (CH 2), 133.0 (C), 139.2 (C), 148.7 (C); MS m/z (relative intensity) 324 (M+ + 2, 0.34), 322 (M+, 1.1), 163 (100). Anal. Calcd for C20H31ClO: C, 74.39; H, 9.68. Found: C, 74.25; H, 9.92.
40
2-{[2-( ) ] }-1- (3c) 3-{[2-(
) ] }-1- (4c) (3c:4c = 91:9)
Ph
O
n-C10H21
OSiMe3
Ph
O
n-C9H19
OSiMe3
3c 4c Bp 165 Υ (bath temp, 0.70 Torr). IR (neat) 1250, 1099, 843 cm-1; 1H NMR (CDCl3) for 3c δ 0.12 (s, 9H),
0.88 (t, J = 7.1 Hz, 3H), 1.21-1.36 (m, 16H), 1.80 (dt, J = 15.5, 7.8 Hz, 1H), 1.92 (dt, J = 15.5, 7.8 Hz, 1H), 3.45 (dt, J = 11.0, 5.6 Hz, 1H), 3.53 (dt, J = 11.0, 5.6 Hz, 1H), 3.76 (t, J = 5.6 Hz, 2H), 4.75 (s, 1H), 4.96 (s, 1H), 5.16 (s, 1H), 7.22-7.35 (m, 5H); 13C NMR (CDCl3) for 3c δ –0.43 (CH3 3), 14.12 (CH3), 22.67 (CH2), 27.51 (CH2), 29.32 (CH2), 29.45 (CH2), 29.50 (CH2), 29.58 (CH2 2), 30.99 (CH2), 31.90 (CH2), 62.03 (CH2), 69.87 (CH2), 85.31 (CH), 111.11 (CH2), 126.89 (CH 2), 127.25 (CH), 128.02 (CH 2), 140.78 (C), 149.34 (C); MS m/z (rel intensity) 390 (M+, 9), 347 (21), 117 (95), 73 (100). Anal. Calcd for C24H42O2Si: C, 73.78; H, 10.84. Found: C, 73.77; H, 10.82. 1- (8): [3482-63-1]27)
n-C10H21
OMe
1H NMR (CDCl3) δ 0.87 (t, J = 6.6 Hz, 3H), 1.19-1.42 (m, 20H), 3.33 (s, 3H), 3.36 (t, J = 6.7 Hz); 13C
NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 26.1 (CH2), 29.3 (CH2), 29.51 (CH2), 29.60 (CH2 2), 29.64 (CH2), 29.66 (CH2 2), 31.9 (CH2), 58.5 (CH3), 72.97 (CH2).
41
1) ∟ 2004, 280. 2) (a) Jin, H.; Uenishi, J.; Christ, W. J.; Kishi, Y. J. Am. Chem. Soc. 1986, 108, 5644. (b) Takai, K.;
Tagashira, M.; Kuroda, T.; Oshima, K.; Utimoto, K.; Nozaki, H. J. Am. Chem. Soc. 1986, 108, 6048. (c) Takai, K.; Kimura, K.; Kuroda, T.; Hiyama, T.; Nozaki, H. Tetrahedron Lett. 1983, 24, 5281.
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Jamison, T. F. Org. Lett. 2000, 2, 4221. (c) Miller, K. M.; Huang, W.-S.; Jamison, T. F. J. Am. Chem. Soc. 2003, 125, 3442. (c) Montgomery, J. Angew. Chem. Int. Ed. 2004, 43, 3890. (d) Moslin, R. M.; Miller-Moslin, K.; Jamison, T. F. Chem. Comm. 2007, 43, 4441.
6) (a) Ng, S.-S.; Jamison, T. F. J. Am. Chem. Soc. 2005, 127, 14194. (b) Ng, S.-S.; Ho, C.-Y.; Jamison, T. F. J. Am. Chem. Soc. 2006, 128, 11513.
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8) Denmark, S. E.; Sweos, R. F. Organosilicon compounds in Cross-coupling Reactions. In Metal-catalyzed Cross-coupling Reactions, 2nd Ed.; de Meijere, A.; Diedrich, F., Eds.; Wiley-VCH: Weinheim, 2004; Chap. 4, pp163-216.
9) (a) Tius, M. A.; Ali, S. J. Org. Chem. 1982, 47, 3163. (b) Blumekopf, T. A.; Bratz, M.; Castañeda, A.; Look, G. C.; Overman, L. E.; Rodriguez, D.; Thompson, A. S. J. Am. Chem. Soc. 1990, 112, 4386. (c) Blumenkopt, T. A.; Look, G. C.; Overman, L. E. J. Am. Chem. Soc. 1990, 112, 4399.
10) Ikenaga, K.; Kikukawa, K.; Matsuda, T. J. Chem. Soc. Perkin. Trans. I 1986, 1959. 11) Miura, K.; Itaya, R.; Horiike, M.; Izumi, H.; Hosomi, A. Synlett 2005, 3148. 12) Schils, R.; Simal, F.; Dermonceau, A.; Noels, A. F.; Eremenko, I. L.; Sidorov, A. A.; Nefedov, S. E.
Tetrahedron Lett. 1998, 39, 7849. 13) Bell, R. A.; Chisholm, M. H.; Couch, D. A.; Rankel, L. A. Inorg. Chem. 1977, 16, 677. 14) (a) Voronkov, M. G.; Druzhdzh, P. V.; Pukhnarevich, V. B. Zh. Obshch. Khim. 1980, 50, 1662; Chem.
Abstr. 1980, 93, 220825h. (b) Voronkov, M. G.; Ushakova, N. I.; Tsykhanskaya, I. I.; Pukhnarevich, V. B. J. Organomet. Chem. 1984, 264, 39. (c) Voronkov, M. G.; Pukhnarevich, V. B.; Ushakova, N. I.; Tsykhanskaya, I. I.; Albanov, A. I.; Vitkovskii, V. Yu. Zh. Obshch. Khim. 1985, 55, 94; Chem. Abstr. 1985, 103, 6399d.
15) (a) Gilges, H.; Schubert, U. Organometallics 1998, 17, 4760. (b) Müller, C.; Lachicotte, R. J.; Jones, W. D. Organometallics 2002, 21, 1190.
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(b) Desai, N. B.; McKelvie, N. J. Am. Chem. Soc. 1962, 84, 1745. 21) Rim, C.; Son, D. Y. Org. Lett. 2003, 5, 3443. 22) Sudo, T.; Asao, N.; Gevorgyan, V.; Yamamoto, Y. J. Org. Chem. 1999, 64, 2494. 23) Miura, K.; Oshima, K.; Utimoto, K. Bull. Chem. Soc. Jpn. 1993, 66, 2356. 24) Urabe, H.; Hamada, T.; Sato, F. J. Am. Chem. Soc. 1999, 121, 2931.
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25) Morrill, C.; Grubbs, R. H. J. Org. Chem., 2003, 68, 6031. 26) Labadie, J. W.; Tueting, D.; Stille, J. K. J. Org. Chem., 1983, 48, 4634. 27) Matsubara, K.; Iura, T.; Maki, T.; Nagashima, H. J. Org. Chem., 2002, 67, 4985.
43
り
さ 1)
(1) (2)
(3) ↓
(4) Ⅴ
500 Υ1,3- ㌹ 2) さ
3)
sp2- - (Scheme 1)
Si-C p ┞ - (Vertical Stabilization) ┞ Si-C p
さ -
(Non-vertical Stabilization) Lambert4 )
Scheme 1
Si
Si ESi E
Si = SiR'3
E Nu
Si
vertical
stabilization
non-vertical
stabilization
or
ぜ
5)
さ TMSOTf TiCl4, AlCl3 Lewis6 )
44
(TBAF) ″ 7)
Lewis - -
syn-(E)- Z syn
(Scheme 2) 8) Scheme 2
(Z)-anti 8a)
レ
Scheme 2
H Me
H
SiMe3
Me3SiMeO
OMe
+cat. Me3SiOTf
O
tBu H
Me
OMe OMe
+
Me H
H
SiMe3
O
H tBu
from (E)-allylsilane
from (Z)-allylsilane
97 : 3
92 : 8
Me
Me3Si
MeO
OMe
Ph+
cat. Me3SiOTf
Ph Ph
OMe OMe
+
from (E)-allylsilane
from (Z)-allylsilane
75 : 25
28 : 72
TS
, -㌹ ぜ よ
anti-SE (Eq. 1) 9)
RE
RZ
Ph
SiH Si = SiR'3
E RE Ph
E HRZSi
Nu RE Ph
E RZ
(1)
ぜ ↓1c) Lewis
り Wender⒢ (–)-Laulimide
45
々 ぜ
(Eq. 2) 10)
O
CHO
H
TBSO
OTBS
O
SiMe3
Me
HH
OiPr
OiPr
O
O
B
O
CF3
CF3
O
O CO2H
(1.0 eq.)
EtCN, –78 °C, 11 h
86% (>90%de)
O
O
Me
H
H
OTBS
TBSO
HO H
O
HO
O
H
O
O
O
H
HHO
HH
Me
(2)
(Scheme 3) 11) 3, 12) Wittig13) ふⅤ
1,3-り (Z)- 14)
1,3-
├
Doyle り レ
(Eqs. 3) 15)
㈻ Ⅴ
Scheme 3
M (X)R
Si-X (M)
R'
Ar3PSi
SiR
R
R Si
R
H-Si
cat.
H-Si
cat.– H2
cat.H-Si, cat,
RCHOAllylsilane
Rh2(pfb)4 or H2PtCl6R SiR'3
pfb = perfluorobutyrate
R'3SiH
R
(3)
46
-- (LnM-H)
- [NiHL4]+, RuHCl(PPh3)3, RhH(CO)(PPh3)3 り (Figure 1)
--
❻ (Figure 2) -
Figure 1. Isomerization via σ-Alkyl Complex
CH CHR
MLnH
CH CHR
MLnH
CH
MLn
CH2R
H2C CH CH2R
MLnH
H2C CH CH2R
H3C
H3C
H3C
Figure 2. Isomerization via π-Allyl Complex
CH CHR
MLn
CH CHR
MLn
H2C CH CH2R
MLn
H2C CH CH2R
CHH2C CHR
MLnH
H3C
H3C
り ┘16) ┘
り17a) り
18)
❻19)
り
ぜ ㈻
り
(Eq. 4) 20) り
り
47
2Cl– OTf– SbF6
–
-Lewis Lewisり 21)
OH
SiMe3
( )n
cat. PtCl2-2AgX
(X= OTf, SbF6)
n = 1, 2
Si = SiMe2R
(4)
OH
SiMe3
( )n
OR1R1CHO ( )n
オ
り
(Scheme 4)
Scheme 4
R SiMe3
R1
OMe
R
Ph
Ph
R
cat. PtCl2-2AgX
(X = OTf, SbF6)
R SiMe3
R1CH(OMe)2
Ph2CHOR2
48
(Z)- 1a (2a) (Table 1) り (10 mol%)
3a (Entry 1) Eq. 42a
3a (Entry 2)
3a (Entry 4)
Table 1. Pt-Catalyzed Reaction Using Various Silver Salts
n-C10H21 SiMe3Ph
OMe
OMe
+
PtCl2 (10 mol%)
AgX (20 mol%)
Ph
OMe
n-C9H191a (2.0 equiv)
3a
CH2Cl2, 24 h
2a
Entry AgX Yield / % dr
1 none 0 –
2 AgOTf 78 63 : 37
3 AgOTs trace –
4 AgSbF6 60 73 : 27
5 AgBF4 8 70 : 30
6 AgPF6 28 72 : 28
(Entries 1–4 in Table 2) 70 Υ 3a よ
(Entry 2) 3a 々
(Entry 3) 40 Υ ス よ ぜ (Entry 4) り さ
3a よ
(Entries 5–7) 40 Υ3a (Entry 6) 70 Υ 3a り
┘
(Entry 7)
49
Table 2. Optimization of Reaction Conditions
n-C10H21 SiMe3Ph
OMe
OMe
+
PtCl2 (10 mol%)
AgX (20 mol%)
Ph
OMe
n-C9H191a (Y equiv)
3a2a
(CH2Cl)2
Entry AgX Temp. / °C Time / h Yield / % dr
1 a AgOTf r.t. 24 78 63 : 37
2 AgOTf 70 1.5 72 61 : 39
3 AgOTf 70 24 Complex mixture.
4 AgOTf 40 12 71 64 : 36
5 a AgSbF6 r.t. 24 60 73 : 27
6 AgSbF6 40 10 89 74 : 26
7 b AgSbF6 70 4 84 63 : 37 aCH2Cl2 was used as solvent. bThe reaction was carried out with PtCl2 (5 mol%), AgSbF6 (10 mol%), and 1a (1.2 equiv).
1a
(Table 3)
4- 2c (Entries 1–5) 2c
々 (Entry 3) ├ 2f 々
2g (Entries 6 and 7)
Table 3. Pt-Catalyzed Reaction of Various Acetals
n-C10H21 SiMe3R
OMe
OMe
+
PtCl2 (X mol%)
AgSbF6 (2X mol%)
R
OMe
n-C9H191a (1.2 equiv)
3
(CH2Cl)2, 70 °C
2
Entry R X Time / h Product Yield / % dr
1 Ph (2a) 5 4 3a 84 63 : 37
2 4-H3C-C6H4 (2b) 10 4 3b 74 69 : 31
3 4-MeO-C6H4 (2c) 5 2 – Complex Mixture
4 4-Cl-C6H4 (2d) 5 10 3d 83 71 : 29
5 4-O2N-C6H4 (2e) 5 24 3e 76 68 : 32
6 n-C8H19 (2f) 10 2 – <20 –
7 c-C6H 11 (2g) 5 2 3g 65 82 : 18
50
┘ 3a (Eq. 5) り
(Eq. 6)
(CH2Cl)270 °C, 2 h
n-C10H21 SiMe3Ph
O
H
+
PtCl2 (10 mol%)
AgSbF6 (20 mol%)
Ph
OMe
n-C9H191a (1.2 equiv)3a, 78% (dr = 60 : 40)
+ HC(OMe)3
(1.2 equiv)
(5)
Ph
OMe
OMePh
O
H
HC(OMe)3+Pt (II)
(6)
2a
(4a) り
1a (Table 4) 5 (Entry 1)
4b
6a (Entry 2) 4c 4d
┘ 6a (Entries 3 and 4) 7 5 6a
Table 4. Reaction of Diphenylmethanol and Its Derivatives
n-C10H21 SiMe3Ph
Ph
OR
+
PtCl2 (10 mol%)
AgOTf (20 mol%)
Ph
Ph
n-C9H191a (2.0 equiv)
5
(CH2Cl)270 °C, 24 h
Ph
Ph
n-C9H19
Ph
Ph
n-C9H19
SiMe3+ +
6a 74a-d
Yield / %
Entry R 5 6a 7
1 H (4a) 48 0 0
2 SiMe3 (4b) 0 72 11
3 Me (4c) 0 79 7
4 Ac (4d) 0 88 3
(Table 5) 4e4f ┘ (Entries 2
and 3) (4g) tert- (4h) (Entries 4 and 5) 4d
51
Table 5. Allylation of Acetates
n-C10H21 SiMe3+
PtCl2 (10 mol%)
AgOTf (20 mol%)
1a (2.0 equiv)(CH2Cl)2
70 °C, 24 h
R
n-C9H19
64d-h
ROAc
Entry R Product Yield / %
1 Ph2CH (4d) 6a 88
2 PhMeCH (4e) 6b 15
3 PhCH2 (4f) 6c 3
4 H2C=CHCH2 (4g) – 0
5 t-Bu (4h) – 0
1a 4b (Table 6) 12 6a 7 8
(Entry 1) 24 8 6a 7 (Etnry 2) 48 6a, 7, 8 5
(Entry 3) Table 6. Reaction of Diphenylmethyl Silyl Ether
n-C10H21 SiMe3Ph
Ph
OSiMe3
+
1a (2.0 equiv) 4b
PtCl2 (10 mol%)
AgOTf (20 mol%)
(CH2Cl)2, 70 °C
Ph
Ph
n-C9H19
5
Ph
Ph
n-C9H19
Ph
Ph
n-C9H19
SiMe3+ +
6a 7
Ph
Ph
n-C9H19
SiMe3
8
+
Yield / %
Entry Time / h 5 6a 7 8
1 12 0 <65 <4 6
2 24 0 72 11 0
3 48 73 0 0 0
Table 6 4b (Scheme 5) り 4b
- 96a 7
8 7 8 6a6a り 5
52
Scheme 5.
Ph
Ph
OSi
Pt (II)
– SiOPt Ph
Ph
+ SiRPt (II)
R Si
Ph
R H H
Si
Ph
Ph
Ph
R5
Ph
Ph
R
Ph
Ph
R
Si +
6a7
Ph
Ph
R
Si
8
– H – Si
H
– Si
Si = SiMe3Si = SiMe3
R = n-C9H19
9
り
2 り
53
Ⅴ
Glass Tube Oven GTO-250 RS Ⅴ (bath temp.) (IR) FT/IR-230 ゝ
(1H NMR, 13C NMR) JEOL JNM-EX270 (1H NMR, 0.00 ppm) (1H NMR (CHCl3), 7.26 ppm) (13C NMR,
77.0 ppm ( )) (1H NMR (C6HD5), 7.16 ppm; 13C NMR, 128.0 ppm ()) ㈻ QP-5050
GC-17A ( DB-1 30.0 m0.25 µl 0.25 mmID 100 kPa 32.5 cm / sec 15
1.40 mL / min 2.5 mL / min N2)
モ
(CH2Cl2) (DCE) ⇩
モ
⇩
⇩ モ
モ オ
1-( )-4- (2b): [3395-83-3]22)
OMe
OMe
Me
2b 4- 23)
(LiBF4, 14.1 mg, 0.15 mmol) 4- (0.60 g, 5.0 mmol) (2.5 mL) (0.68 mL, 6.5 mmol) 40 Υ 3
(10 mL) (10 mL 3)
54
⇩
(110 Υ / 2.6 Torr) 2b 93% 1H NMR (C6D6) δ 2.10 (s, 3H), 3.16 (s, 6H), 5.36 (s, 1H), 7.17 (d, J = 8.0 Hz, 2H), 7.51 (d, J = 8.0 Hz, 2H) ; 13C NMR (C6D6) δ 21.1 (CH3), 51.9 (CH3 2), 102.9 (CH), 127.2 (CH 2), 129.0 (CH 2), 136.1 (C), 137.9 (C) ; MS m/z (relative intensity) 166 (M+, 3.8), 135 (M+ – MeO, 100). 1-( )-4- (2c): [2186-92-7]22)
OMe
OMe
MeO
2c 4- 2b 1H NMR (C6D6) δ 3.16 (s, 6H), 3.28 (s, 3H), 5.38 (s, 1H), 6.81 (dt, J = 8.5, 2.0 Hz, 2H), 7.51 (dt, J = 8.5, 2.0 Hz, 2H) ; 13C NMR (C6D6) δ 51.8 (CH3 2), 54.7 (CH3), 102.8 (CH), 113.8 (CH 2), 128.5 (CH 2), 131.1 (C), 160.2 (C) ; MS m/z (relative intensity) 182 (M+, 6.1), 151 (M+ – MeO, 100). 1- -4-( ) (2d): [3395-81-1]22)
OMe
OMe
Cl
2d 4- 2b 1H NMR (CDCl3) δ 3.31 (s, 6H), 5.38 (s, 1H), 7.32–7.41 (m, 4H); 13C NMR (CDCl3) δ 52.5 (CH3 2), 102.2 (CH), 128.1 (CH 2), 128.3 (CH 2), 134.2 (C), 136.6 (C) ; MS m/z (relative intensity) 188 (M++2, 1.2), 186 (M+, 4.6), 155 (100). 1-( )-4- (2e): [881-67-4]22)
OMe
OMe
O2N 2e 4- 2b 1H NMR
(CDCl3) δ 3.34 (s, 6H), 5.48 (s, 1H), 7.64 (d, J = 8.8Hz, 2H), 8.23(d, J = 8.8Hz, 2H); 13C NMR (CDCl3) δ 52.6 (CH3 2), 101.5 (CH), 123.3 (CH 2), 127.8 (CH 2), 145.0 (C), 147.9 (C) ; MS m/z (relative intensity) 197 (M+, 0.44), 166 (M+ – MeO, 100). 1,1- (2f): [18824-63-0]24)
n-C8H17
OMe
OMe
2f 2b 1H NMR (C6D6) δ 0.90 (t, J = 6.4 Hz, 3H), 1.25–1.41 (m, 12H), 1.66 (td, J = 6.8, 5.6 Hz, 2H), 3.18 (s, 6H), 4.35 (t, J = 5.6 Hz, 1H); 13C NMR (CDCl3) δ 14.3 (CH3), 23.1 (CH2), 25.1 (CH2), 29.5 (CH2), 29.9 (CH2), 30.0 (CH2), 32.3 (CH2), 32.9 (CH2), 52.0 (CH3 2), 104.6 (CH); MS m/z (relative intensity) 156 (M+ – MeOH, 2.3), 71 (100).
55
(2g): [18231-08-8]25) OMe
OMe
2g 2b 1H
NMR (C6D6) δ 0.96–1.24 (m, 5H), 1.57–1.72 (m, 4H), 1.89–1.94 (m, 2H), 3.16 (s, 6H), 3.94 (d, J = 7.2 Hz, 1H); 13C NMR (CDCl3) δ 26.2 (CH2 2), 26.8 (CH2), 28.4 (CH2 2), 40.3 (CH), 53.0 (CH3 2), 108.5 (CH); MS m/z (relative intensity) 127 (M+ – MeO, 6.4), 75 (100).
( ) (4b): [14629-59-5]26)
Ph
Ph
OSiMe3
4b 27)
(1.84 g, 10.0 mmol) (25.4 mg, 0.1 mmol) (40 mL) (HMDS, 1.67 mL, 8.0 mmol)
(10 mL) 5 5
(125 Υ / 0.81 Torr) ( ) (4b, 2.44g, 9.5 mmol) 95% 1H NMR (CDCl3) δ
0.07 (s, 9H), 5.75 (s, 1H), 7.18–7.35 (m, 10H); 13C NMR (CDCl3) δ 0.1 (CH3 3), 76.5 (CH), 126.5 (CH 4), 127.0 (CH 2), 128.2 (CH 4), 144.8 (C 2) ; MS m/z (relative intensity) 256 (M+, 31), 167 (M+ – OSiMe3, 100), 73 (100).
(4c): [1016-09-7]28)
Ph
Ph
OMe 4c 29) ◢ (III) 9
(162 mg, 0.40 mmol) (3.68 g, 20 mmol) (0.89 mL, 22 mmol) 80 Υ 1
(110 Υ / 0.58 Torr) (4c, 1.41 g. 7.1 mmol) 36% 1H NMR (CDCl3) δ 3.38 (s, 3H), 5.24 (s, 1H), 7.21–7.37 (m,
10H); 13C NMR (CDCl3) δ 57.0 (CH3), 85.4 (CH), 126.9 (CH 4), 127.4 (CH 2), 128.4 (CH 4), 142.0 (C2) ; MS m/z (relative intensity) 198 (M+, 88), 167 (M+ – OMe, 100).
(4d): [954-67-6]30)
Ph
Ph
OAc 4d
(3.68 g, 20.0 mmol) (7.27 mL, 90.0 mmol) (7.27 mL, 76.9 mmol) 18
(100 mL) TBME (50 mL 3) (50 mL2) 1N (50 mL) (50 mL) (50 mL)
⇩ (128 Υ /
56
0.62 Torr) (4d, 4.40 g, 19.4 mmol) 97% 1H NMR (CDCl3) δ 2.17 (s, 3H), 6.88 (s, 1H), 7.25–7.38 (m, 10H); 13C NMR (CDCl3) δ 21.2 (CH3), 76.9 (CH), 127.0 (CH 2), 127.8 (CH 2), 128.4 (CH 4), 140.1 (C 2), 169.9 (C) ; MS m/z (relative intensity) 226 (M+, 16), 165 (100).
(1- ) (4e): [93-92-5]31)
Ph
Me
OAc 4e 1- 4b 1H NMR
(CDCl3) δ 1.54 (d, J = 6.6 Hz, 3H), 2.07 (s, 3H), 5.88 (q, J = 6.6 Hz, 1H), 7.24–7.36 (m, 5H); 13C NMR (CDCl3) δ 21.3 (CH3), 22.2 (CH3), 72.3 (CH), 126.1 (CH 2), 127.8 (CH), 128.5 (CH 2), 141.6 (C), 170.3 (C).
Schlenck (0.025 mmol)
(0.050 mmol) 1,2- (1.5 mL) (0.50 mmol)
(0.60 mmol) 70 Υ ス
り
┘ 3-[ ( ) ]-1- (3a)
Ph
OMe
n-C9H19 Bp 149 Υ (bath temp., 1.2 Torr). 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.3 Hz, 3H),
1.19–1.32 (m, 16H), 2.29–2.38 (m, 1H), 3.21 (s, 3H), 4.01 (d, J = 6.4 Hz, 1H), 4.84 (dd, J = 17.1, 1.8 Hz, 1H), 4.92 (dd, J = 10.2, 2.0 Hz, 1H), 5.47 (ddd, J = 17.1, 10.2, 9.2 Hz, 1H), 7.21–7.36 (m, 5H); for the minor isomer δ 3.19 (s, 3H), 4.02 (d, J = 6.4 Hz, 1H), 4.94 (dd, J = 17.1, 2.0 Hz, 1H), 5.06 (dd, J = 10.3, 2.0 Hz, 1H), 5.63 (ddd, J = 17.1, 10.3, 9.1 Hz, 1H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.6 (CH2 2), 29.7 (CH2), 30.0 (CH2), 31.9 (CH2), 50.9 (CH), 57.0 (CH3), 87.2 (CH), 116.2 (CH2), 127.3 (CH), 127.6 (CH 2), 127.9 (CH 2), 139.0 (CH), 140.4 (C); for the minor isomer δ 51.0 (CH), 127.4 (CH), 127.5 (CH 2), 128.0 (CH 2), 139.5 (CH), 140.6 (C); MS m/z (relative intensity) 256 (M+ – MeOH, 0.38), 121 (100). 3-[ (4- ) ]-1- (3b)
Me
OMe
n-C9H19
Bp 161 Υ (bath temp., 1.9 Torr). 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.7 Hz, 3H), 1.13–1.33 (m, 16H), 2.29–2.37 (m, 1H), 2.35 (s, 3H), 3.17 (s, 3H), 3.97 (d, J = 6.6 Hz, 1H), 4.95 (dd, J =
57
17.1, 2.1 Hz, 1H), 5.06 (dd, J = 10.4, 2.0 Hz, 1H), 5.63 (ddd, J = 17.1, 10.4, 9.1 Hz, 1H), 7.11–7.16 (m, 4H); for the minor isomer δ 2.34 (s, 3H), 3.19 (s, 3H), 4.85 (dd, J = 17.2, 2.1 Hz, 1H), 4.92 (dd, J = 10.4, 2.1 Hz, 1H), 5.47 (ddd, J = 17.2, 10.4 9.4 Hz, 1H). 3-[(4- ) ]-1- (3d)
Cl
OMe
n-C9H19
Bp 152 Υ (bath temp., 1.1 Torr). IR (neat) 1491, 1466, 1092 cm-1; 1H NMR (CDCl3) for the major isomer δ 0.87 (t, J = 6.7 Hz, 3H), 1.16–1.34 (m, 16H), 2.21–2.34 (m, 1H), 3.19 (s, 3H), 3.97 (d, J = 6.3 Hz, 1H), 4.83 (dd, J = 17.1, 2.0 Hz, 1H), 4.93 (dd, J = 10.4, 2.1 Hz, 1H), 5.43 (ddd, J = 17.1, 10.4, 9.2 Hz, 1H), 7.15 (d, J = 8.4 Hz, 2H), 7.26–7.32 (m, 2H); for the minor isomer δ 3.18 (s, 3H), 4.01 (d, J = 6.1 Hz, 1H), 4.91 (dd, J = 17.1, 2.0 Hz, 1H), 5.05 (dd, J = 10.4, 1.8 Hz, 1H), 5.59 (ddd, J = 17.1, 10.4, 9.1 Hz, 1H), 7.18(d, J = 8.2 Hz, 2H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.1 (CH2), 29.3 (CH2), 29.5 (CH2), 29.7 (CH2 2), 30.0 (CH2), 31.9 (CH2), 50.9 (CH), 57.0 (CH3), 86.5 (CH), 116.6 (CH2), 128.1 (CH2), 128.9 (CH 2), 133.0 (C), 138.5 (CH), 138.9 (C); for the minor isomer δ 51.1 (CH), 116.5 (CH2), 128.2 (CH 2), 138.9 (CH), 139.2 (C); MS m/z (relative intensity) 290 (M+ – MeOH, 1.7), 155 (100). 3-[ (4- ) ]-1- (3e)
O2N
OMe
n-C9H19
Bp 195 Υ (bath temp., 0.95 Torr). IR (neat) 1523, 1346, 1105 cm-1; 1H NMR (CDCl3) for the major
isomer δ 0.87 (t, J = 6.9 Hz, 3H), 1.20–1.35 (m, 16H), 2.26–2.37 (m, 1H), 3.23 (s, 3H), 4.10 (d, J = 6.6 Hz, 1H), 4.81 (dd, J = 17.1, 1.8 Hz, 1H), 4.94 (dd, J = 10.0, 1.8 Hz, 1H), 5.43 (dt, J = 17.1, 10.0 Hz, 1H), 7.40 (d, J = 8.8 Hz, 2H), 8.19 (d, J = 8.8 Hz, 2H); for the minor isomer δ 4.84 (dd, J = 17.3, 2.0 Hz, 1H), 5.04 (dd, J = 10.3, 1.5 Hz, 1H), 5.57 (dt, J = 17.3, 10.3 Hz, 1H), 7.41(d, J = 8.9 Hz, 2H), 8.20 (d, J = 8.9 Hz, 2H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.55 (CH2 2), 29.58 (CH2), 29.9 (CH2), 31.9 (CH2), 51.0 (CH), 57.4 (CH3), 86.4 (CH), 117.2 (CH2), 123.2 (CH 2), 128.2 (CH2), 138.0 (CH), 147.3 (C), 148.5 (C); for the minor isomer δ 51.1 (CH), 57.5 (CH3), 86.2 (CH), 123.2 (CH2), 128.1 (CH 2), 137.9 (CH), 148.6 (C); MS m/z (relative intensity) 301 (M+ – MeOH, 0.38), 166 (100). Anal. Calcd for C20H31NO3: C, 72.04; H, 9.37; N, 4.20. Found: C, 72.18; H, 9.60; N, 4.38. 3-[( )( ) ]-1- (3g)
OMe
n-C9H19 Bp 147 Υ (bath temp., 2.9 Torr). 1H NMR (CDCl3) for the major isomer δ 0.88 (t, J = 6.6 Hz, 3H),
0.96–1.80 (m, 27H), 2.14–2.22 (m, 1H), 2.72 (dd, J = 6.3, 5.3 Hz, 1H), 3.42 (s, 3H), 4.98 (dd, J = 16.8, 2.0 Hz, 1H), 5.01 (dd, J = 10.4, 2.2 Hz, 1H), 5.60 (ddd, J = 16.8, 10.4, 9.5 Hz, 1H); for the minor isomer δ 4.96 (dd, J = 17.6, 2.3 Hz, 1H), 5.04 (dd, J = 10.5, 2.1 Hz, 1H), 5.69 (ddd, J = 17.6, 10.5, 9.6 Hz, 1H); 13C NMR (CDCl3) for the major isomer δ 14.1 (CH3), 22.7 (CH2), 26.3 (CH2), 26.6 (CH2 2), 27.3 (CH2), 27.4 (CH2), 29.27 (CH2), 29.34 (CH2), 29.63 (CH2), 29.66 (CH2), 29.8 (CH2), 30.8 (CH2), 31.9 (CH2), 40.9 (CH), 47.2
58
(CH), 61.6 (CH3), 90.0 (CH), 115.2 (CH2), 141.0 (CH); for the minor isomer δ 41.2 (CH), 46.7 (CH), 89.5 (CH), 115.7 (CH2), 139.3 (CH); MS m/z (relative intensity) 262 (M+ – MeOH, 0.65), 127 (88), 95 (100). 2- -1,1- -1- (5)
Ph
Ph
n-C9H19 Bp 188 Υ (bath temp., 1.1 Torr). 1H NMR (CDCl3) δ 0.88 (t, J = 6.7 Hz, 3H), 1.00 (t, J = 7.5 Hz, 3H),
1.11–1.41 (m, 14H), 2.10 (t, J = 7.8 Hz, 2H), 2.13 (q, J = 7.5 Hz, 2H), 7.12–7.30 (m, 10H); 13C NMR (CDCl3) δ 13.4 (CH3), 14.1 (CH3), 22.7 (CH2), 24.8 (CH2), 28.5 (CH2), 29.3 (CH2), 29.4 (CH2), 29.5 (CH2), 29.6 (CH2), 31.2 (CH2), 31.9 (CH2), 126.0 (CH 2), 127.90 (CH 2), 127.95 (CH 2), 129.25 (CH 2), 129.32 (CH 2), 137.5 (C), 140.9 (C), 143.50 (C), 143.58 (C); MS m/z (relative intensity) 334 (M+, 24), 91 (100). 3-( )-1- (6a)
Ph
Ph
n-C9H19 Bp 206 Υ (bath temp., 1.2 Torr). IR (neat) 1495, 1452, 910 cm-1; 1H NMR (CDCl3) δ 0.87 (t, J = 6.7 Hz,
3H), 1.21–1.39 (m, 16H), 2.81–2.92 (m, 1H), 3.72 (d, J = 10.6 Hz, 1H), 4.87 (dd, J = 16.8, 1.8 Hz, 1H), 4.90 (dd, J = 10.6, 1.8 Hz, 1H), 5.44 (ddd, J = 16.8, 10.6, 9.1 Hz, 1H) 7.03–7.31 (m, 10H); 13C NMR (CDCl3) δ 14.1 (CH3), 22.7 (CH2), 27.0 (CH2), 29.3 (CH2), 29.5 (CH2), 29.6 (CH2 2), 31.9 (CH2), 32.8 (CH2), 47.9 (CH), 57.3 (CH), 116.0 (CH2), 125.9 (CH), 126.1 (CH), 128.1 (CH 4), 128.45 (CH 2), 128.53 (CH 2), 141.2 (C 2),.144.1 (CH); MS m/z (relative intensity) 334 (M+, 0.51), 167 (100).
59
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