Centre in Green Chemistry and Catalysis, Department of Chemistry, Université de Montréal, Station Downtown, Canada.
Chemistry. 2012 Nov 12;18(46):14784-91. doi: 10.1002/chem.201202528. Epub 2012 Sep 25.
Herein, we report the enantio- and diastereoselective formation of trans-iodo- and trans-chlorocyclopropanes from α-iodo- and α-chlorozinc carbenoids by using a dioxaborolane-derived chiral ligand. The synthetically useful iodocyclopropane building blocks were derivatized by an electrophilic trapping of the corresponding cyclopropyl lithium species or a Negishi coupling to give access to a variety of enantioenriched 1,2,3-substituted cyclopropanes. The synthetic utility of this method was demonstrated by the formal synthesis of an HIV-1 protease inhibitor. In addition, the related stereoselective bromocyclopropanation was also investigated. New insights about the relative electrophilicity of haloiodomethylzinc carbenoids are also presented.
在此，我们报告了使用二氧硼烷衍生的手性配体，从α-碘代和α-氯代锌卡宾通过对映选择性和非对映选择性形成反式-碘代和反式-氯代环丙烷。通过相应的环丙基锂物种的亲电捕获或 Negishi 偶联对合成有用的碘环丙烷构建块进行衍生化，可获得各种对映体富集的 1,2,3-取代环丙烷。该方法的合成实用性通过 HIV-1 蛋白酶抑制剂的形式合成得到了证明。此外，还研究了相关的立体选择性溴环丙烷化。还提出了卤代碘甲基锌卡宾相对亲电性的新见解。
