Enantioselective Decarboxylative Allylation of Carbazolones and Indolones: Formal
Synthesis of (–)-Kopsihainanine A
Christopher J. Gartshore and David W. Lupton
Monash University, Clayton 3800, Victoria, Australia
Since its discovery in 1965 the nucleophilic substitution of allylic compounds has undergone significant
advancements. As it stands, the enantioselective decarboxylative allylation reaction (DcA) is one of the most
powerful tools for the construction of enantioenriched quaternary carbon containing molecules,1 however
until recently it was limited to either ketone or ester derived enolates. 2
This presentation focuses on the use of enantioselective DcA to construct a broad range of C3-substituted
carbazolone and indolone structures, as well as their subsequent derivatization to useful synthetic
intermediates for the synthesis of aspidosperma alkaloids. 3
We will also report the use of this method for the first enantioselective formal synthesis of (-)-kopsihainanine
A.4,5
O
O
R
N
Pg
O
O
enantioselective
DcA
17 examples up to 93% ee
R
N
Pg
O
O
O
HO
N
R
N
Pg
N
Pg
N
H
(-)-kopsihainanine A
1
Weaver, J. D., Recio III, A., Grenning, A. J. Tunge, J. A. Chem. Rev. 2011, 111, 1846
Behenna, D. C., Liu, Y., Yurino, T. Kim, J., White, D. E., Virgil, S. C., Stoltz, B. M. Nature Chem. 2012, 4,
130.
3 Gartshore, C. J. Lupton, D. L. 2012, manuscript under review
4 Chen, J., Chen, J. –J., Yao, X., Gao, K. Org. Biomol. Chem. 2011, 9, 5334
5 Jing, P., Yang, Z., Zhao, C., Zheng, H., Fang, B., Xie, X. and She, X. Chem. Eur. J. 2012, 18, 6729
2
39th Annual Synthesis Symposium
5th December 2014
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