Double Addition of Alkynyllithium Reagents to Amides/Lactams: A Direct and Flexible Synthesis of 3-Amino-1,4-diynes Bearing an Aza-Quaternary Carbon Center
Double Addition of Alkynyllithium Reagents to Amides/Lactams: A Direct and Flexible Synthesis of 3-Amino-1,4-diynes Bearing an Aza-Quaternary Carbon Center
复制标题
炔基锂试剂与酰胺/内酰胺的双重加成：直接灵活合成带有氮杂季碳中心的 3-氨基-1,4-二炔
DOI：
10.1021/acs.joc.9b01416
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发表时间：
2019-07-19
影响因子：
3.6
通讯作者：
Huang, Pei-Qiang
中科院分区：
文献类型：
--
作者：
Chen, Hang;Huang, Ying-Hong;Huang, Pei-Qiang
以叔胺和内酰胺为原料，建立了一种高效、温和的直接、灵活地合成含氮杂季碳的3-氨基-1，4-二炔的方法。一锅法包括用三氟甲磺酸原位活化酰胺，然后在二氯甲烷中以0.5mol.L~(-1)的浓度双重加入炔基锂试剂。这构成了酰胺的直接还原双烷基化方法的扩展，该方法允许使用炔基锂试剂作为第一加成亲核试剂，并将炔基作为第一引入基团。
An efficient and mild protocol for the direct and flexible synthesis of 3-amino-1,4-diynes bearing an aza-quaternary carbon from tertiary amides and lactams has been established. The one-pot method consists of in situ activation of amides with trifluoromethanesulfonic anhydride, followed by double addition of alkynyllithium reagents at a concentration of 0.5 mol.L-1 in dichloromethane. This constitutes an extension of the method of direct reductive bisalkylation of amides that allows both employing alkynyllithium reagents as the first-addition nucleophiles and incorporating an alkynyl group as the first- introduced group.