Stereodivergent α-Allylation of Linear Aldehydes with Dual Iridium and Amine Catalysis
Stereodivergent α-Allylation of Linear Aldehydes with Dual Iridium and Amine Catalysis
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DOI：
10.1021/ja5003247
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发表时间：
2014-02-26
影响因子：
15
通讯作者：
Carreira, Erick M.
中科院分区：
文献类型：
--
作者：
Krautwald, Simon;Schafroth, Michael A.;Carreira, Erick M.
我们描述了完全立体发散，双催化α -烯丙基化的线性醛。反应是通过直接铱催化外消旋烯丙基醇与原位生成的胺取代进行的。使用Ir（P，烯烃）配合物和二芳基硅基脯氨醇醚作为催化剂，在磷酸二甲基氢作为启动子的存在下，对于获得高对映选择性和非对映选择性（>99% ee，高达>20:1 dr）至关重要。该方法的实用性在抗抑郁药(-)-帕罗西汀的简明对映选择性合成中得到了证明。
We describe the fully stereodivergent, dual catalytic alpha-allylation of linear aldehydes. The reaction proceeds via direct iridium-catalyzed substitution of racemic allylic alcohols with enamines generated in situ. The use of an Ir(P,olefin) complex and a diarylsilyl prolinol ether as catalysts in the presence of dimethylhydrogen phosphate as the promoter proved to be crucial for achieving high enantio- and diastereoselectivity (>99% ee, up to >20:1 dr). The utility of the method is demonstrated in a concise enantioselective synthesis of the antidepressant (-)-paroxetine.