手性四唑并[1,5-a]氮杂环庚烷通过杂芳基苄基阴离子中间体的非对映选择性烷基化。
Diastereoselective Alkylations of Chiral Tetrazolo[1,5-]azepines via Heterobenzylic Anion Intermediates.
机构信息
Department of Chemistry, New York University, 100 Washington Square East, New York, New York 10003, United States.
出版信息
Org Lett. 2022 Sep 23;24(37):6722-6727. doi: 10.1021/acs.orglett.2c02445. Epub 2022 Sep 12.
Abstract
The alkylations of chiral seven-membered rings fused to tetrazoles are highly diastereoselective. The diastereoselectivity depended on the placement and the size of the substituent on the ring and on the electrophile. Subsequent alkylations occurred with high stereoselectivity, allowing for the construction of quaternary stereocenters. Computational studies revealed that torsional effects are responsible for the observed diastereoselectivities. Substituted products can be reduced to the corresponding secondary amines, thus providing an approach for synthesizing diastereomerically enriched azepanes.
摘要
稠合至四唑的手性七元环的烷基化反应具有高度的非对映选择性。非对映选择性取决于环上取代基的位置和大小以及亲电试剂。随后的烷基化反应具有高立体选择性，允许构建季立体中心。计算研究表明，扭转效应是导致观察到的非对映选择性的原因。取代产物可以还原为相应的仲胺，从而为合成非对映体富集的氮杂环庚烷提供了一种方法。
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