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Nickel-Catalyzed Decarbonylative Addition of Anhydrides to Alkynes Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008, 130, 17226 Current Literature Kalyani Patil 12/20/08 O O O + Pr Pr Ni(cod) 2 (10 mol%), PMe 3 (40 mol%) ZnCl 2 (20 mol%), MeCN, 80 °C O O Pr Pr Kalyani Patil @ Wipf Group Page 1 of 13 12/27/2008
Transcript of Nickel-Catalyzed Decarbonylative Addition of …ccc.chem.pitt.edu/wipf/Current...
Nickel-Catalyzed Decarbonylative Addition
of Anhydrides to Alkynes
Kajita, Y.; Kurahashi, T.; Matsubara, S.
J. Am. Chem. Soc. 2008, 130, 17226
Current Literature
Kalyani Patil
12/20/08
O
O
O
+ Pr Pr
Ni(cod)2 (10 mol%), PMe3 (40 mol%)
ZnCl2 (20 mol%), MeCN, 80 °C
O
O
Pr
Pr
Kalyani Patil @ Wipf Group Page 1 of 13 12/27/2008
Outline
• Synthesis of Isocoumarins
• Nickel - LA Catalyzed Reactions
• Title Paper
• Summary
Kalyani Patil @ Wipf Group Page 2 of 13 12/27/2008
Synthesis of Isocoumarins/!-Pyrones
Fukuyama, T.; Higashibeppu, Y.; Yamaura, R.; Ryu, I. Org. Lett. 2007, 9, 587
Nakamura, Y.; Ukita, T. Org. Lett. 2002, 4, 2317
[3+2+1] cycloaddition
TMS
R
O
C
R1
O [Ru]O
R1R
TMS
O
TMS
Ph
C8H17
O
+
Ru3(CO)12 (6 mol%)Et2MeN.HI (20 mol%)
toluene, 160 °CCO 20 atm
O
C8H17Ph
TMS
O
PO(OEt)2
EtO2C
N2 Rh2L4
PO(OEt)2
EtO2C
Rh2L4
H-X
ElX
EtO2C H
PO(OEt)2
Elbase
X
EtO2C
PO(OEt)2
El
EtO2C
XEtO2C
H-X
El
CO2H
Ph
O PO(OEt)2
EtO2C
N2
1. , Rh2(OAc)4
2. DBU/toluene, 81%
O
O
Ph
CO2Et
Kalyani Patil @ Wipf Group Page 3 of 13 12/27/2008
Synthesis of Isocoumarins
Larock, R. C.; Doty, M. J.; Han, X. J. Org. Chem. 1999, 64, 8770
I
OMe
O
+ H3C C(CH3)3
Pd(OAc)2, Na2CO3
LiCl, DMF, 100 °C, 72%
O
O
CH3
C(CH3)3
X = I, Br, and OTf
X
OR
O
O
O
R2
R1
O
OR+X-
R2
R1
PdX
OR
OR1 R2
OR
O
R2
PdX
R1
Pd
O
-X+RO
R1R2
Pd(0) Pd(OAc)2
Kalyani Patil @ Wipf Group Page 4 of 13 12/27/2008
Synthesis of Isocoumarins
Luo, T.; Schreiber, S. L. Angew. Chem. Int. Ed. 2007, 46, 8250
R3
OH
O
R2
O
R1
O
O
R2
R1
R3
[M+]
[3,3]
O
C
O
R2
R1
R3
6-endo dig
[M+]
O
O
[M]
R3R2
H
R1
O
O
R3R2
R1
O
O
R3R2
R1
Nu
or
O
O
[(Ph3P)AuCl]/AgSbF6, CH2Cl2
reflux, 12 h, 74%
O
O
O
O
+
OMe
OMeMeO
[(Ph3P)AuCl]/AgSbF6, CH2Cl2
rt, 24 h, 82%
O
O
MeO
MeO
OMe
Kalyani Patil @ Wipf Group Page 5 of 13 12/27/2008
Examples of Nickel-LA Catalyzed Reactions
Ikeda, S-i.; Mori, N.; Sato, Y. J. Am. Chem. Soc. 1997, 119, 4779
Nakao, Y.; Yada, A.; Ebata, S.; Hiyama, T. J. Am. Chem. Soc. 2007, 129, 2428
O
H
TBSO+
1. Ni(acac)2, PPh3, Me3Al THF, rt
2. DBU, air, >98%
O OTBS
OTBS
Cyclic cotrimerization of !,"-enones and alkynes
Carbocyanation of alkynes
R CN + Pr PrNi(cod)2, ligand, LA
toluene, 80 °C
R
Pr Pr
CN
entry substrate ligand LA product (yield)
1.
MeO
CNPPhMe2 AlMe2Cl (96%)
MeO
Pr
CN
Pr
2.Ph
CN dppb BPh3 (94%)
Ph
Pr
CN
Pr
3. Me CN PPh2(t-Bu) AlMe3 (71%)
Pr
Me CN
Pr
Kalyani Patil @ Wipf Group Page 6 of 13 12/27/2008
Decarbonylative Cross Coupling of Cyclic Anhydrides
O’Brien, E. M.; Bercot, E. A..; Rovis, T. J. Am. Chem. Soc. 2003, 125, 10498
O
O
O
R1
R1 H
H
MLn
MLn
O
O
O
R1
R1
H
H
-CO
+COMLn
O
O
R1
R1 H
H
MR2
R2
CO2HR1
R1 H
H
O
O
O i) Nickel complex, THF, 66 °C, 3 h
ii) Ph2Zn (2 equiv.), 4-F styrene (1 equiv.) THF, 66 °C, 12 h Ph
CO2H+
CO2H
PhO
Ni(COD)2/neocuproine (1:1)
Ni(COD)2/neocuproine/dppb (1.5:1.0:0.5)
66:33
>95:5 (77% yield)
Ni
O
O
O
N
NNi
O
O
OC N
N
P
PNi
P
PNi CO Ni
O
O
N
N
Ph2Zn
Ph
CO2H
Kalyani Patil @ Wipf Group Page 7 of 13 12/27/2008
Decarbonylative Addition of Phthalimides to Alkynes
Kajita, Y.; Matsubara, S.; Kurahashi, T. J. Am. Chem. Soc. 2008, 130, 6058
C N
C N
O
MC M N
-M
C N
carboamination
direct oxidativeaddition
addition/decarbonylation
N
O
O
+ RL RS
Ni(cod)2 (10 mol%), PMe3 (40 mol%)
toluene, 110 °C
N
O
RL
RS
Ar
Ar
entry phthalimide time (h) product (yield)
1.N
O
O
7 N
O
Pr
Pr
(84%)
N
O
O
2. 7N
O
Pr
Pr
(72%)
N
O
O
3. 12N
O(93%)
2:1
alkyne
C6F5
C6F5
N
N
PrPr
PrPr
N
N
Kalyani Patil @ Wipf Group Page 8 of 13 12/27/2008
Title Paper - Optimization Studies
Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008, 130, 17226
O
O
O
+ Pr Pr
Ni(cod)2 (10 mol%), PMe3 (40 mol%)
additive (20 mol%), MeCN, 80 °C, 12 h
O
O
Pr
Pr1.2 eq
entry additive yield (%) entry additive yield (%)
1. - 12 7. LiCl 76
2. 96 8. Bu4NPF6 54ZnCl2
3. 92 9. Bu4NCl 72
4. 91 10. Bu4NOTf 67ZnBr2
Zn(OTf)2
5. 90 11. Bu4NBr 65
6. 92 12. Bu4NI 52BPh3
ZnI2
Kalyani Patil @ Wipf Group Page 9 of 13 12/27/2008
Ni Catalyzed Decarbonylative Addition of Anhydrides
Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008, 130, 17226
entry substrate time (h) product (yield)
1.O
O
O
15 O
O
Pr
Pr
(87%)
O
O
O
2. 18O
O
Pr
Pr
(82%)
O
O
O
3. 18O
O
Pr
Pr
O
O
Pr
Pr
(61%) (29%)
O
O
O
4. 18O
O
Pr
Pr
O
O
Pr
Pr
(53%) (8%)
5. O
O
O
O
O
Pr
Pr
(94%)15
O
O
O
6. 18O
O
Pr
Pr
(23%)
Kalyani Patil @ Wipf Group Page 10 of 13 12/27/2008
Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008, 130, 17226
entry alkyne time (h) product (yield)
1. 12
2. 15
3. 15
O
O
(91%)(1:1)
4. 15
5. 18
6. 24
Ph Ph O
O
Ph
Ph
(87%)
OMe
O
O
(75%)(1:1)OMe
O
O
(89%)(2:1)
TMSO
O
TMS
93%
TMS Ph O
O
TMS
Ph
86%
Ni Catalyzed Decarbonylative Addition of Anhydrides
Kalyani Patil @ Wipf Group Page 11 of 13 12/27/2008
Title Paper - Plausible Mechanism
Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008, 130, 17226
C
OO
C
O
M C
OM
-M
C
O
oxa-metallacycle
direct oxidative addition
O
O
O
+RS RL O
O
RL
RS+ Ni(0)Ln + ZnCl2
NiLn
O
O
RL
RS
NiLn
O
O
RS
RL
favored
disfavored
+ Ni(0)Ln + ZnCl2
NiLn
O
O
RL RS
ZnCl2
Kalyani Patil @ Wipf Group Page 12 of 13 12/27/2008
Summary
• Synthesis of Isocoumarins/!-Pyrones in Good Yields
• Nickel Catalyzed Decarbonylative Addition of Cyclic
Anhydrides to Alkynes
• Terminal Alkynes failed to Convert to the Product
Kalyani Patil @ Wipf Group Page 13 of 13 12/27/2008
