indium in organic synthesis huang-jianzhou 2012-04-14
DESCRIPTION
化合价： 0, +1,+2, s2 5p1 J. Uziel, Synthesis, 2007, Scott E. Denmark, Chem. Rev. 2003, 103, 2763 Basi V. Subba Reddy, Eur. J. Org. Chem. 2010, 591 Sujit Roy, Chem. Rev. 2010, 110, 2472 Anthony J. Downs, Chem. Rev. 2007, 107, 2 Advantages indium in organic synthsis : stable in air and water Notoxicity for man Low first ionization potential, can be an effective single electron transfer agent organoindium reagents are easy prepared 1 、 IntroductionTRANSCRIPT
Indium in Organic Synthesis
Huang-Jianzhou2012-04-14
1 、 Introduction
2 、 Preparation of Allylindium
3 、 As Lewis Acid
4 、 Cross coupling
5 、 Reduction
6 、 Conclusion
化合价： 0, +1,+2,+3
1863
5s2 5p1J. Uziel, Synthesis, 2007, 1739.Scott E. Denmark, Chem. Rev. 2003, 103, 2763Basi V. Subba Reddy, Eur. J. Org. Chem. 2010, 591Sujit Roy, Chem. Rev. 2010, 110, 2472Anthony J. Downs, Chem. Rev. 2007, 107, 2
Advantages indium in organic synthsis:
stable in air and waterNotoxicity for manLow first ionization potential, can be an effective single electron transfer agentorganoindium reagents are easy prepared
1 、 Introduction
4
IO OH
+In, DMF,rt
Yasuo Butsugan, J. Org. Chem., 1988, 53, 1831
PhCHOI
+In, DMF,rt
Ph
OH
89%
87%
PhCHOBr
+In, H2O,80℃
Ph
OH
97%
T. H. Ghan, Tetrahedron Lett. 1991, 32, 7017
In 1988,
In 1991
2In + 2BrCH2CO2Et BrInCH2CO2Et
CH2CO2EtPhCHO
Ph
OHCO2Et
xylene83%
Reuben D. Rieke, J. Org. Chem, 1975 , 40, 2253
Ph Br PhCHO+
Ph
OH
Ph
In, H2O88% yieldanti : syn = 96:4
R2
R1
X In+ R2
R1
InR1
R2In
InOR2
R
R1
InO R
R1
R2
R CHO
Tak-Tang Chan, Tetrahedron Lett. 1995, 36, 8957
Regioselectivity
5
6
Br
F FPhCHO+
In, H2O
100%Ph
OH
F F
Feng-Ling Qing, Tetrahedron Lett. 1998, 54, 14198
O
H BrIn, H2O
OH OH
¦Á-adduct ¦Ã-adduct
yield = 85 %(¦Á : ¦Ã = 99 : 1)
Teck-Peng Loh, Tetrahedron Lett. 2001, 42, 8701
OI In
TMSCl THF
+ +
OO
O
Br
In, THF, 0℃ to rt
OHO
O
Leo A. Paquette, J. Org. Chem. 1996, 61, 7492
O
100%
THFOH
Phil Ho Lee,Tetrahedron Lett, 2001, 42 , 37
or CuI
Diastereoselectivity
8
Cy
OTBS
H
OTBSH
O
Br In, H2O
OTBS
OH
OTBS
OH+ +
anti : syn = 3.9:1
yield = 90 %
OHH
O
Br In, H2O+
yield = 85 %
OH
OH
OH
OH+
anti : syn = 1 : 9.8
O
H
InO
H
O
Cy H
In
InO
OHCy
TS-a TS-b
Cram rule
Leo A. Paquette, J. Am. Chem. soc. 1996, 118, 1931
9
In0
X X
H2O org solvInⅠ InⅢ
XInⅢ
X
x
TmⅡ
Xorg solv
InⅡ X
TmⅡ
X
H2O
InⅠ Inx
TmⅡ
X InⅢ XInⅠ xX
InⅢ x3 Mgm *InⅢ X3-n
n
n = 1, 2, 3
2 、 Preparation of Allylindium
Pd0
PdⅡ
X
X
PdⅡ
InX X
InX
InX
X
X
X = OAc, Cl, OPhOCOOEt, OH
+ InI, Pd(PPh3)4 Ph
OH43%-100%
Shuki Araki, Org. Lett. 2000, 2 , 847
PhCHO
11
NO
O
Pd0N
Pd
O
COMeInI
N
Pd
O
COMe
In I
Pd0
InO
N
I
COMePhCHO
In
NO
HI
RCOMe
In
NO
RI
HCOMe
NR
OHHO
O
NR
OHHO
O
NO
O
PhCHO+Pd(OAc)2, PPh3, InI
THF/H2O
NR
OHHO
O
NR
OHHO
O
Org. Lett., 2009, 11 , 1293Marvin J. Miller, J. Org. Chem., 2003, 68, 139
PhCHO+InI
Ni(acac)2(10%mol)
PPh3, THF, rt, 4h
OH
PhPh
OH
Tsunehisa Hirashita, Chem Commun, 2006, 2595
Ph
OH
Ph
OHPh
OH
4%
36%
54%
In,Ni(0), H+
In,Ni(0), PhCHO
Ni
H+H
Ni InI HInL2
PhCHO
1
2
3
1
NiO
Ph
InO Ni
In
InI
Ph
OInL2 InL2
Ph
OInL2 InL2
2
3
13
allenesI CHO
MeO+
allene(1 bar)DMF, In, Pd(PPh3)4
OH
OMe
Ronald Grigg, Chem Commun, 2000, 645
64%
Pd(0) R1X
R1PdX
R2
R2
Pd XR1
R1
PdX
In
R2
R1
Pd
R2
In
R1
InXR2RCHO
R1
R2
OHR
14
NTs
O
PhI+In(1.2eq), Pd(OAc)2(5mol%)
OP3
10mol%, DMF
N
Ph
OHTs
H
H
N
Ph
OHTs
H
H
cis(80%) trans(13%)
I
O
Pd(PPh3)4
DMF, InO+
O
OH
50%, dr = 1.2:1
I
N
N
O
Ph
+
allene(1 bar)DMF, In, Pd(0)
61% NO
HNPh
Ph
Ronald Grigg, Chem Commun, 2002, 1372
Suk-Ku Kang, J. Org. Chem. 2002, 67, 4376
In
+
X
orgnic solvent(DMF or THF)
ionic liquid
InⅠ InⅢ
In
Me Br I
BrIn
BrIn
BrMe Me
Me
IIn
IIn
I
DMF
InⅠ
H2O
InⅢX
X
Araki, J. Org. Chem. 1988, 53, 1831
Tak Hang, J. Am. Chem. Soc. 1999, 121, 3228 J. Org. Chem. 2007, 72, 923
The reactivity of the allyl halide ： I ≈ Br >> Cl, F inactive
allylindium intermediate
16
OEtBr
OH
PhCHO+In(2eq),H2O, rt OEt
OH
HOPh
95 % (de = 100%)
Yves Canac, J. Org. Chem. 2001, 66, 3206Leo A. Paquette, J.Org. Chem. 1999, 64, 217
Br O
OPhCHO+
In, H2O/THF
91%syn : anti = 85 :15
Ph
OH
OCOCH3
Br
OOH
PhCHO+
1. In/THF-H2O2. 6N HCl
75 %
OO
Ph
Prabir K. Choudhury, Tetrahedron Lett. 1998, 39, 3581
Shuki Araki, J. Org. Chem. 1999, 64, 172
PhCHOClCl + In, LiI, DMF
83% Ph
OH
Cl
syn : anti = 92:8
Addition to C=O Bonds
NH
O
OBr
In(2eq), THF/H2O(1:1)
0¡æ, 2h NH
OH
O
100%Benito Alcaide, J. Org. Chem. 2005, 70, 3198
Subodh Kumar, Tetrahedron Lett, 2003, 44 , 2101
NH
CHOBr
NBn
+ +In, THF/H2O(2:1)
30¡æ
NH
NBn
93 % yield
Teck-Peng Loh, Org. Lett., 1999, 1 , 1855
Br + PhCHO
(+)-cinchonine(2eq), In(2eq)THF/n-hexane(3:1)
-78 to 25¡æ,2hPh
OH
73% yield72 % ee
N
NHO
Tetrahedron Lett ,1999, 40, 9333Tetrahedron Lett, 1999, 40, 9115
Br + PhCHO
ligand(2.6eq), In(10eq)Ce(OTf)4¡¤xH2O
EtOH/H2O(1:1)25¡æ,2h
Ph
OH
90% yield92 % ee
NON N
O
iPrPri
PhCHO + BrIn(2eq), ligand(2eq), py(2eq)
THF/n-hexane, -78¡æ, 1.5h Ph
OH
99 % yield93% ee
L. C. Hirayama, Tetrahedron Lett , 2005, 46, 2315
NH2
Ph
HO
Ph
Asymmetry
Addition to C=N Bonds
X
In+
Ph
NPh OH
Ph
N
H
PhO
X = Br, DMF-H2O,rt
Ph
NHSO2Ph
H
X = Br, THF, rtPh
NHSO2Ph
90%
88 %
NH
NOMe
X = Br, H2O, rt
N
HNOMe
EtO2C CN
Ph
X = I, THF, rt
EtO2C
Ph
NH265%
70%
N
ClCO2Ph
N
OPh
O
92%
X = Br, THF,rtPh
N
H
HN
p-tolSO2
X = Br,DMF-H2O, rt
89 %Ph
NHHN
p-tolSO2
N
Ph
CH2OH
HN
Ph
CH2OH
71%
X = I, THF, rtPh H
NS
O
ONMe2
X = Br,THF, rt
Ph
HNS
O
ONMe2
90%
Ph H
NN
OO
X
3eq
In(0)(2eq), 4A MS,THF, 0 to rt
ligand(10mol %)
+
Ph
HNN
OO
SO2CF3
SO2CF3
OHOH
X = I, 95%(88% ee)
X = Br, 82%(90% ee)
J. Am. Chem. Soc. 2007, 129, 3846
Ph H
NN
OO
I
3eq
In(0)(2eq), 4A MS,THF, 0 to rt
ligand(X mol %)
+
Ph
HNN
OO CF3
CF3
OHOH
X = 10 mol %, 77%(70%ee)X = 100mol%, 72%(84%ee)
Org Lett, 2005, 7, 2767
Ph H
NN
OO
I+
i-Pr
In(0)(2eq), 4A MS
THF, 0 to rtPh
HNN
OO
i-Pr99%(dr > 99;1)
Gregory R. Cook, Org Lett, 2004, 6, 1741
Asymmetry
Ar H
NNHBz
Br+
In(0)(1.5eq)catalyst(10 mol%)
0℃, Ar
HNNHBz CF3
F3C NH
NH
O
HNS O
But
Eric N. Jacobsen, Angew. Chem. Int. Ed. 2007, 46, 1315
Ar = Ph, 87%(91% ee)
Ar = p-ClC6H4, 83%(92 %)
Ar = o-BrC6H4, 78%(93%)
N
O NO H PF6
Ph H
NNHBz
Br+
In(0)(1.5eq)catalyst(10 mol%)
0℃, Ph
HNNHBz
94%(99 % ee)
Doo Ok Jang, J. Am. Chem. Soc. 2010, 132, 12168
Ph H
NNH
PhO
+B(pin)
InI(5mol%), ligand(5mol%)24h,tol/CH3OH, 0℃
Ph
HNNH
PhO
99%(98:2 er)
B(pin)
Me
InI(10mol%), ligand(10mol%)CH2Cl2/CH3CH2OH, 0℃
Ph
HNNH
PhO
Ph
HNNH
PhO
anti synα α
anti : syn = 19:185%,
97:3 er
Ph H
NNH
PhO
+
Shu Kobayashi, Angew. Chem. Int. Ed. 2010, 49, 1838
B(pin)
R
Lewis baseInL LIn
R
CNO
N HN
OPh
Ph
Ph
Ph
Addition to C-C Multiple Bonds
BuBr+
In, THF, rt Bu
86%Brindaban C. Ranu, Chem Commun, 1997, 1225
HOIn2Br3
3+
100℃, DMFOH OH+
91% yield85 : 35
Yasuo Butsugan, J. Org. Chem. 1995, 60, 1841
Shuki Araki, J. Am. Chem. Soc. 1996, 118, 4699
OHIn2x3+
DMF, 140℃, 4hOH
44%(100%)
OMe NROH NR
InR4
R5 H
O HR1
R2
H
R3
InR4
R5 H
O HR1
R2
H
R3
24
Other ways
MgBr InBr3Ph
In
3
CN
CNPh
DMFPh
Ph
CN
CN
yield = 76 %
Shuki Araki, Tetrahedron Lett. 1999, 4, 2331
H
O
SnBu3+
InCl3OH
Meacetone, -78 to rt
90 %yieldanti : syn = 98:2
James A. Marshall, J. Org. Chem. 1995, 60, 1920-1921
PhCHO OAc+InI, Ni(acac)2, PPh3
rt, 1hPh
OH97 % yield
Shuki Araki, J. Org. Chem. 2004, 69, 5054
3 、 As Lewis Acid
O
C8H17
OC2H5
O In(OTf)3(5mol%)3A MS,Acetyene(1atm)
solvent free, 100¡ãC, 36h
O
OC2H5
O
C8H17
25.4g 90%
Org Lett. 2005, 7, 3279
Eiichi Nakamura, J. Am. Chem. Soc. 2003, 125, 13002
O
OC2H5
OPh H+
In(OTf)3(5mol%)
neat, 100-140¡ãC
O
OC2H5
O
Ph99%
J. Am. Chem. Soc. 2008, 130, 4492
OEt
ONHs-Bu
MeO
Ph H+
1)In(OTf)3(10mol%)BuLi(10mol%), 120, 8h
2)aq AcOH/THF
O
OC2H5
O
Ph92%(94% ee)
J. Org. Chem. 2010, 75, 8322
Veronique Michelet,Org Lett. 2010, 12, 2582
O
H
MeO2C CO2Me
InCl3(20mol%)(Cy)(i-Pr)NH(20mol%)
DCE,80¡ãC
OHCMe
CO2MeCO2Me
82%
N
H
MeO2C CO2Me
InCl3
Cy i-Pr
Coniaene reaction
Eiichi Nakamura, J. Am. Chem. Soc. 2008, 130, 17161
CO2Me
NPMB
CO2MeO In(OTf)3 (5 mol%), DBU (5 mol%)
toluene, reflux
NO
PMB
CO2MeCO2Me
90%
In(OTf)3
DBU TfOH-DBU
R2
NOR1 O
MeO
OIn(OTf)2
MeO
R3
ON
OO
In OTfOTf
R3
R1
R2
MeO
MeO
Susumi Hatakeyama, Angew. Chem. Int. Ed. 2008, 47, 6244
COOMeEtOOC In(OTf)3(10mol %)
60 °C, 24 h, neat
EtOOC COOMe
99%
MeO
O O
+
In(NTf2)3(1mol%) EtO2C
EtO2Ctol, 150
98%
O O
OR2R1
LnIn
Eiichi Nakamura, Org Lett. 2009, 11, 1845
O
MePh
InI3(0.2eq) p-TSA(0.05eq), H2O(0.95)
DCM,rtO
MeO
Ph
O
46 %Proposed Mchanistic Pathway
O
RAr
In
O
In
ArR
H2O
O
ArR
In
OH
OH
ArR
O
H+
OH
ArR
O
ORO
Ar
O
John K. Snyder, Org Lett. 2011, 13, 4280
Aldol, Minnich, D-A Reaction
+ 4Cl-PhNH2
H
H
OTMSInCl3(20%)
H2O
NH
H
O
Teck-Peng Loh, Tetrahedron , 2000, 56, 3227
OMe
TMSOH
O
+1) ligand-In(OTf)3(5mol%)
PhOMe
2) TFA O
O
Ph
Xiaoming Fen, Angew. Chem. Int. Ed. 2008, 47, 1308
96%(98% ee)trans : cis < 1:20
NNO O
NHO
PhPh
OHN
PhPh
Org Lett. 2011, 13, 3668
H
OHO
O+
Cl
H
HO
O 63%
Shu Kobayashi, Tetrahedron Lett, 1998, 39 ,1579
PhCHO +OSiMe3 InCl3, rt,neat
10min
OH O
61%
Teck-Peng Loh, J. Am. Chem. Soc. 2008, 130, 16492
EtH
O
O
+In(OTf)3(5mol%)ligand(6mol%)
4A MS, DCE,rt5d
OHOEt
O
NON N
OH
H
H
H
96%(95% ee)
Carbonyl-ene Reactions
Ph H CHO NHBn2+ + InCl3, tol, 120°C
98%
H
O
Ph
InBr3(10mo;%)(R)-Binol(10mol%)
Cy2NMe(50mol%)CH2Cl2,40°C
OH
Ph
95%(98% ee)
Masakatsu Shibasaka, J. Am. Chem. Soc. 2005, 127, 13760
NBn2
Ph
Lei Wang, J. Org. Chem. 2009, 74, 4364
5 、 Cross-Coupling
Teck-Peng Loh, Angew. Chem. Int. Ed. 2011, 50, 511
Luis A. Sarandeses, Org Lett. 1999, 1, 1267
Ph3InX
Me
+Pd(Ph3P)2Cl2
THF, refluxMe
96%
J. Am. Chem. Soc. 2001, 123, 4155
3 3
Ph3InAc
X+
Pd(Ph3P)2Cl2
THF, reflux Ac
X = OTf, 95%X = Br, 91%
Paul Knochel, Angew. Chem. Int. Ed. 2009, 48, 2236
Aiwen Lei, J. Am. Chem. Soc. 2008, 130, 9429
Paul Knochel, Angew. Chem. Int. Ed. 2008, 47, 7648
Teck-Peng Loh, J. Am. Chem. Soc. 2010, 132, 15852
Et
O In(0.8eq)/InCl3(0.4eq)
CH3CN/H2O, 82%Et
O In O
Et
Cl
Ph
O
Cl
PdCl2(PPh3)2, THF, reflux, 24hEt
OPh
O
83%
2In + InCl3
Umpolung
I
AcPdCl2(PPh3)2, LiClDMA. 100¡ãC, 24h
Ac
O
Org Lett. 2011, 13, 422
3InCl
Akio Baba, Synlett, 1999, 182
J. Org. Chem. 2001, 66, 7741-
Ph Ph
OMe2SiClH +
InCl3(5mol%)
CH2Cl2,25°C Ph Ph
99%
Cl
O
Cl
OH
Ph2SiClH +
77%
InCl3(5mol%)
(CH2Cl)2,80°C
4 、 Reduction
Reductive Aldol Reaction
Akio Baba, Angew. Chem. Int. Ed. 2004, 43, 711
Ph
O
Me
MeO
CHO+
Et3SiHInBr3(10mol%)
EtCN, 0¡ãC, 4hPh
O OSiEt3
OMe
75%,syn : anti = 90 : 10
InBr3 + Et3SiH
HInBr2
+Et3SiBr
+
OInBr2
Ph CH3
O
InBr3O
HAr
H
Ph
Ph
O OInBr2
OMe
Et3SiH
Ph
O OSiEt3
OMe
Ph
O
Me
Akio Baba., Angew. Chem. Int. Ed. 2011, 50, 8623
Ph OH
O
OMe
OSiMe3 InBr3(MeO)3SiH
CH2Cl2,rt Ph
O
OMe
O
90 %
R1 OH
OInBr3HSi(OMe)3
R1 O
OBr3In
H Si(OMe)3HInBr3, H2
R1 O
OSi
OMem n
InBr3
R2
R3OR4
OSiMe3
InBr3Me3Si(OMe)3
R1
O
R2 R3OR4
O
6 、 Conclusion
Indium and its salts provide various methodologies for formation C-C bond, with high reactivity and the unique selectivity;Work is still ongoing, especially in enantioselective reactions.
