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Catalytic asymmetric addition of an amine N-H bond across internal alkenes

机译：催化不对称在内烯烃中添加胺N-H键

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摘要

Hydroamination of alkenes, the addition of the N-H bond of an amine across an alkene, is a fundamental, yet challenging, organic transformation that creates an alkylamine from two abundant chemical feedstocks, alkenes and amines, with full atom economy(1-3). The reaction is particularly important because amines, especially chiral amines, are prevalent substructures in a wide range of natural products and drugs. Although extensive efforts have been dedicated to developing catalysts for hydroamination, the vast majority of alkenes that undergo intermolecular hydroamination have been limited to conjugated, strained, or terminal alkenes(2-4); only a few examples occur by the direct addition of the N-H bond of amines across unactivated internal alkenes(5-7), including photocatalytic hydroamination(8,9), and no asymmetric intermolecular additions to such alkenes are known. In fact, current examples of direct, enantioselective intermolecular hydroamination of any type of unactivated alkene lacking a directing group occur with only moderate enantioselectivity(10-13). Here we report a cationic iridium system that catalyses intermolecular hydroamination of a range of unactivated, internal alkenes, including those in both acyclic and cyclic alkenes, to afford chiral amines with high enantioselectivity. The catalyst contains a phosphine ligand bearing trimethylsilyl-substituted aryl groups and a triflimide counteranion, and the reaction design includes 2-amino-6-methylpyridine as the amine to enhance the rates of multiple steps within the catalytic cycle while serving as an ammonia surrogate. These design principles point the way to the addition of N-H bonds of other reagents, as well as O-H and C-H bonds, across unactivated internal alkenes to streamline the synthesis of functional molecules from basic feedstocks.Hydroamination with high enantio- and regioselectivity is achieved across a wide range of internal alkenes by using a cationic iridium complex that adds an ammonia surrogate containing a pyridine group.
机译：烯烃的水胺，在烯烃上加入胺的N-H键，是一种基本，但具有挑战性的有机转化，产生来自两种丰富的化学原料，烯烃和胺的烷基胺，具有全原子经济（1-3）。反应尤其重要，因为胺，尤其是手性胺，在各种天然产物和药物中是普遍的子结构。虽然广泛的努力已经专用于开发催化剂的水醋酸催化剂，但是大多数经历分子压氨基的烯烃已被限制为缀合，应变或末端烯烃（2-4）;通过直接加入胺的N-H键在未追死的内烯烃（5-7）中的N-H键的直接添加，包括光催化催化水中的胺（8,9），并且已知不对称分子间添加该烯烃。实际上，目前的直接倾向解的肾上腺分子分子与缺乏指导基团的任何类型的未致死烯烃的分子聚酰胺的实例仅发生中等映射性（10-13）。在这里，我们报告了一种阳离子铱系统，其催化了一系列未致死的内烯烃的分子间水，包括共循环和环状烯烃的那些，以提供高对映选择性的手性胺。催化剂含有亚甲基甲硅烷基取代的芳基和三氟乙烯偶联的膦配体，反应设计包括2-氨基-6-甲基吡啶作为胺，以增强催化循环内的多个步骤的速率，同时用作氨代理。这些设计原理指出了在未致死的内烯烃中添加其他试剂的NH键的方法，以简化来自碱性原料的功能分子的合成。通过高肾上腺素和区域选择性的氢胺。通过使用阳离子铱络合物，可以添加含有吡啶基团的氨代理的宽范围的内烯烃。

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  • 来源
    《Nature》 |2020年第7837期|254-260|共7页
  • 作者

    Xi Yumeng; Ma Senjie; Hartwig John F.;

  • 作者单位

    Univ Calif Berkeley Dept Chem Berkeley CA 94720 USA|Lawrence Berkeley Natl Lab Div Chem Sci Berkeley CA 94720 USA;

    Univ Calif Berkeley Dept Chem Berkeley CA 94720 USA|Lawrence Berkeley Natl Lab Div Chem Sci Berkeley CA 94720 USA;

    Univ Calif Berkeley Dept Chem Berkeley CA 94720 USA|Lawrence Berkeley Natl Lab Div Chem Sci Berkeley CA 94720 USA;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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  • 正文语种 eng
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