Roger Adams Laboratory, Department of Chemistry , University of Illinois , Urbana , Illinois 61801 , United States.
J Am Chem Soc. 2019 Dec 4;141(48):19161-19170. doi: 10.1021/jacs.9b11261. Epub 2019 Nov 19.
The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this article, we describe the first enantioselective, diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a bistosyl urea as the bifunctional nucleophile and fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the dichlorination reported previously. Furthermore, the -stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.
烯烃的对映选择性、偕二氨基化反应是有机合成中仍然存在的一个具有挑战性的立体控制加成反应。这个问题的通用解决方案将能够有效地和选择性地制备广泛应用的、手性富集的二胺，用于药物化学和催化领域。在本文中，我们描述了首例通过手性、对映富集的有机硒催化剂与双（对甲苯磺酰基）脲作为双官能团亲核试剂以及氟-collidinium 四氟硼酸盐作为化学计量氧化剂介导的简单烯烃的对映选择性、偕二氨基化反应。带有各种取代基的二芳基、芳基-烷基和烷基-烷基烯烃都以一致的高对映选择性但可变的产率进行双氨基化。该反应可能通过类似于先前报道的二氯化作用的 Se(II)/Se(IV) 氧化还原催化循环进行。此外，该转化的 -立体特异性为没有强烈的空间位阻或电子偏见的烯烃的高对映选择性二氨基化反应提供了希望。
