不对称[1,2]-锂炔加成到羰基与 II 型阴离子接力化学的合并。
Merging Asymmetric [1,2]-Additions of Lithium Acetylides to Carbonyls with Type II Anion Relay Chemistry.
机构信息
Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
出版信息
Org Lett. 2019 Sep 20;21(18):7655-7659. doi: 10.1021/acs.orglett.9b02959. Epub 2019 Sep 9.
Abstract
An enantioselective three-component coupling reaction has been developed, enabling the union of a variety of lithium acetylides and electrophiles exploiting an achiral linchpin via an anionic reaction cascade. This Type II Anion Relay Chemistry tactic is initiated via an enantioselective [1,2]-carbonyl addition exploiting BINOL catalysis to access an enantioenriched alkoxide intermediate. Migration of charge across the linchpin via a [1,4]-Brook rearrangement with electrophile capture affords a three-component propargyl ether adduct. Herein, we report the development, scope, and limitations of this reaction sequence.
摘要
已开发出一种对映选择性的三组分偶联反应，通过阴离子反应级联，利用手性连接子使各种锂炔化物和亲电试剂结合。这种类型 II 阴离子接力化学策略是通过对映选择性的[1,2]-羰基加成反应启动的，利用BINOL 催化作用来获得手性富集的烷氧基中间体。通过[1,4]-Brook 重排使电荷跨越连接子迁移，并与亲电试剂捕获，得到三组分炔丙基醚加合物。本文报道了该反应序列的发展、范围和局限性。
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