Rhodium-catalyzed asymmetric nitroallylation of arylmetallics with cyclic nitroallyl acetates and applications in organic synthesis
Rhodium-catalyzed asymmetric nitroallylation of arylmetallics with cyclic nitroallyl acetates and applications in organic synthesis
复制标题
DOI：
10.1002/ejoc.200600275
复制
发表时间：
2006-09-11
影响因子：
2.8
通讯作者：
Gong, Liu-Zhu
中科院分区：
文献类型：
--
作者：
Dong, Lin;Xu, Yan-Jun;Gong, Liu-Zhu
本文报道了铑催化的芳基硼酸和芳基氯化锌与环状硝基烯丙基乙酸酯的高对映选择性硝基烯丙基化反应。催化剂筛选结果表明，[Rh（OH）（COD）]（2）与光学纯的binap的铑配合物是芳基硼酸与2-硝基环己-2-烯基酯硝基烯丙基化反应的最佳催化剂，Rh（acac）（C_2H_4）（2）与（R）-binap合成的铑配合物有效地催化了芳基氯化锌与2-硝基烯丙基的硝基烯丙基化反应。以高达93%的高产率和高达96%ee的高对映体选择性在0 ℃下制备硝基环己-2-烯基乙酸酯。光学纯（+）-β-石蒜烷和（+）-γ-石蒜烷的简明全合成方法，总收率分别为53%和52%。通过用乙酸2-硝基环己-2-烯基酯对3，4-亚甲二氧基苯基氯化锌进行不对称硝基烯丙基化反应来实现总收率。((c)Wiley-VCH Verlag GmbH & Co. KGaA，69451魏因海姆，德国，2006）。
Highly enantioselective rhodium-catalyzed nitroallylations of arylboronic acids and arylzinc chlorides with cyclic nitroallyl acetates are described. Catalyst screening indicated that the rhodium complex of [Rh(OH)(COD)](2) and optically pure binap is the optimal catalyst for the nitroallylation of arylboronic acids with 2-nitrocyclohex-2-enyl esters, providing good yields and high enantioselectivities of up to 99% ee. The rhodium complex prepared from Rh(acac)(C2H4)(2) and (R)-binap efficiently catalyzed the nitroallylation of arylzinc chlorides with 2-nitrocyclohex-2-enyl acetate at 0 degrees C in high yields of up to 93% and with high enantioselectivities of up to 96% ee. A number of synthetically useful intermediates with high optical purity were prepared with this reaction as starting point: concise total syntheses of optically pure (+)-beta-lycorane in 53% overall yield and of (+)-gamma-lycorane in 52% overall yield were achieved by commencing with the asymmetric nitroallylation of 3,4-methylenedioxyphenylzinc chloride with 2-nitrocyclohex-2-enyl acetate. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).