Amines bearing γ-stereocenters are highly important structural motifs in many biologically active compounds. However, reported enantioselective syntheses of these molecules are indirect and often require multiple steps. Herein, we report a general asymmetric route for the one-pot synthesis of chiral γ-branched amines through the highly enantioselective isomerization of allylamines, followed by enamine exchange and subsequent chemoselective reduction. This protocol is suitable for establishing various tertiary stereocenters, including those containing dialkyl, diaryl, cyclic, trifluoromethyl, difluoromethyl, and silyl substituents, which allows for a rapid and modular synthesis of many chiral γ-branched amines. To demonstrate the synthetic utility, Terikalant and Tolterodine are synthesized using this method with high levels of enantioselectivity.

中文翻译：

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通过铑催化的还原胺化反应不对称合成γ-支化胺。

在许多生物活性化合物中，带有γ-立体中心的胺是非常重要的结构基序。但是，据报道这些分子的对映选择性合成是间接的，通常需要多个步骤。在这里，我们报告了通过烯丙胺的高度对映选择性异构化，然后进行烯胺交换和随后的化学选择性还原，一锅合成手性γ-支化胺的一般不对称路线。该协议适用于建立各种叔立体中心，包括那些含有二烷基，二芳基，环状，三氟甲基，二氟甲基和甲硅烷基取代基的立体中心，从而可以快速且模块化地合成许多手性γ-支化胺。为了证明合成的实用性，使用这种方法以高水平的对映选择性合成了特立卡兰和托特罗定。