Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst.

Enantioselective Intermolecular Addition of Aliphatic Amines to Acyclic Dienes with a Pd-PHOX Catalyst.
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DOI:
10.1021/jacs.7b03480
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发表时间:
2017-05-31
影响因子:
15
通讯作者:
Malcolmson SJ
Malcolmson SJ
中科院分区:
化学1区
文献类型:
--
作者:
Adamson NJ;Hull E;Malcolmson SJ

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我们报道了一种脂肪胺与无环1,3 - 二烯进行催化、对映选择性分子间加成的方法。在大多数情况下,在含有5 mol%带有PHOX配体的钯催化剂存在下,反应在室温或低于室温时能高效进行,生成的烯丙基胺的对映体比例(er)高达97:3。配体中缺电子膦的存在不仅使催化剂更具活性,而且对在该转化中实现高位点选择性至关重要。
We report a method for the catalytic, enantioselective intermolecular addition of aliphatic amines to acyclic 1,3-dienes. In most cases, reactions proceed efficiently at or below room temperature in the presence of 5 mol % of a Pd catalyst bearing a PHOX ligand, generating allylic amines in up to 97:3 er. The presence of an electron-deficient phosphine within the ligand not only leads to a more active catalyst but also is critical for achieving high site selectivity in the transformation.
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