手性和非对映选择性催化 2-氮杂二烯的环丙烷化反应，用于合成具有季碳手性中心的氨基环丙烷。
Catalytic Enantio- and Diastereoselective Cyclopropanation of 2-Azadienes for the Synthesis of Aminocyclopropanes Bearing Quaternary Carbon Stereogenic Centers.
机构信息
Department of Chemistry , Duke University , Durham , North Carolina 27708 , United States.
出版信息
Org Lett. 2019 Sep 20;21(18):7380-7385. doi: 10.1021/acs.orglett.9b02692. Epub 2019 Aug 29.
Abstract
We report the catalytic enantio- and diastereoselective preparation of aminocyclopropanes by the cyclopropanation of terminal and ()-internal 2-azadienes with donor/acceptor carbenes derived from α-diazoesters. The resulting cyclopropanes bear quaternary carbon stereogenic centers vicinal to the amino-substituted carbon and are formed as a single diastereomer in up to 99:1 er and 97% yield with 0.5 mol % of Rh(DOSP) and only 1.5 equiv of the diazo reagent. Transformations with internal azadienes afford cyclopropanes with three contiguous stereogenic centers.
摘要
我们报告了通过末端和（）-内 2-氮杂二烯与源自α-重氮酯的给体/受体卡宾的环丙烷化反应，催化对映选择性和非对映选择性地制备氨基环丙烷。得到的环丙烷在氨基取代的碳原子的相邻位置带有季碳原子手性中心，并且在 Rh(DOSP)的 0.5 mol%和仅 1.5 当量的重氮试剂存在下以高达 99:1 的 er 和 97%的收率形成单一非对映异构体。与内氮杂二烯的转化得到具有三个连续手性中心的环丙烷。
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