手性铑配合物催化芳基硼酸与硝基烯丙基乙酸酯的不对称硝基烯丙基化反应及其在光学纯（+）-γ-石蒜碱简洁全合成中的应用。

Asymmetric nitroallylation of arylboronic acids with nitroallyl acetates catalyzed by chiral rhodium complexes and its application in a concise total synthesis of optically pure (+)-gamma-lycorane.

作者信息

Dong Lin, Xu Yan-Jun, Cun Lin-Feng, Cui Xin, Mi Ai-Qiao, Jiang Yao-Zhong, Gong Liu-Zhu

机构信息

Key Laboratory for Asymmetric Synthesis and Chirotechnology of Sichuan Province, Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, 610041, China.

出版信息

Org Lett. 2005 Sep 15;7(19):4285-8. doi: 10.1021/ol051795n.

DOI:10.1021/ol051795n

PMID:16146408

Abstract

[reaction: see text]A new rhodium-catalyzed highly enantioselective nitroallylation of 2-nitrocyclohex-2-enol esters with arylboronic acids is described. A rhodium complex of [RhOH(COD)]2 and optically pure BINAP is the optimal catalyst that provides good yields and high enantioselectivities ranging from 90 to 99% ee for various arylboronic acids at 50 degrees C. A concise total synthesis of optically pure (+)-gamma-lycorane in overall 38% yield was achieved on the basis of this new method.

摘要

[反应：见正文] 描述了一种新的铑催化的2-硝基环己-2-烯醇酯与芳基硼酸的高度对映选择性硝基烯丙基化反应。[RhOH(COD)]₂与光学纯BINAP的铑配合物是最佳催化剂，在50℃下，对于各种芳基硼酸，能提供良好的产率和90%至99% ee的高对映选择性。基于这种新方法，以38%的总产率实现了光学纯(+)-γ-石蒜碱的简洁全合成。