Suresh Rahul, Massad Itai, Marek Ilan
Schulich Faculty of Chemistry, Technion - Israel Institute of Technology Technion City 3200009 Haifa Israel
Chem Sci. 2021 Jun 9;12(27):9328-9332. doi: 10.1039/d1sc02575a. eCollection 2021 Jul 14.
The Cope rearrangement of 2,3-divinyloxiranes, a rare example of epoxide C-C bond cleavage, results in 4,5-dihydrooxepines which are amenable to hydrolysis, furnishing 1,6-dicarbonyl compounds containing two contiguous stereocenters at the 3- and 4-positions. We employ an Ir-based alkene isomerization catalyst to form the reactive 2,3-divinyloxirane with complete regio- and stereocontrol, which translates into excellent control over the stereochemistry of the resulting oxepines and ultimately to an attractive strategy towards 1,6-dicarbonyl compounds.
2,3-二乙烯基环氧乙烷的科普重排是环氧碳-碳键断裂的一个罕见例子，生成4,5-二氢氧杂环庚三烯，该产物易于水解，得到在3-和4-位含有两个相邻立体中心的1,6-二羰基化合物。我们使用一种基于铱的烯烃异构化催化剂，以完全的区域和立体控制形成反应性的2,3-二乙烯基环氧乙烷，这转化为对所得氧杂环庚三烯立体化学的出色控制，并最终成为合成1,6-二羰基化合物的一种有吸引力的策略。
