Enantioselective construction of all-carbon quaternary stereocenters using palladium-catalyzed asymmetric allylic alkylation of γ-acetoxy-α,β-unsaturated carbonyl compounds
Enantioselective construction of all-carbon quaternary stereocenters using palladium-catalyzed asymmetric allylic alkylation of γ-acetoxy-α,β-unsaturated carbonyl compounds
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DOI：
10.1002/adsc.200505149
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发表时间：
2005-10-01
影响因子：
5.4
通讯作者：
Hamada, Y
中科院分区：
文献类型：
--
作者：
Nemoto, T;Fukuda, T;Hamada, Y
我们已经成功地证明，γ-乙酰氧基-α，β-不饱和羰基化合物是有用的起始原料Pd催化的不对称烯丙基烷基化，以构建全碳四元立体中心。使用2-5 mol %的Pd催化剂和4-10 mol %的β-手性二氨基氧化膦，在Zn（OAC）（2）的存在下，用衍生自环状β-酮酯的各种前手性亲核试剂进行γ-乙酰氧基-α，β-不饱和羰基化合物的不对称烯丙基烷基化，提供具有高达95%ee的全碳季立体中心的相应产物。
We have successfully demonstrated that gamma-acetoxy-alpha,beta-unsaturated carbonyl compounds are useful starting materials for Pd-catalyzed asymmetric allylic alkylation to construct all-carbon quaternary stereocenters. With the use of 2-5 mol % of Pd catalyst and 4-10 mol % of P -chirogenic diaminophosphine oxides, asymmetric allylic alkylation of gamma-acetoxy-alpha,beta-unsaturated carbonyl compounds with various prochiral nucleophiles derived from cyclic beta-keto esters proceeded in the presence of Zn(OAC)(2), providing the corresponding products with an all-carbon quaternary stereocenter in up to 95% ee.