Albright Haley, Vonesh Hannah L, Schindler Corinna S
Department of Chemistry, Willard Henry Dow Laboratory, University of Michigan, 930 North University Avenue, Ann Arbor, Michigan 48109, United States.
Org Lett. 2020 Apr 17;22(8):3155-3160. doi: 10.1021/acs.orglett.0c00917. Epub 2020 Apr 3.
An intermolecular carbonyl-olefin metathesis reaction is described that relies on superelectrophilic Fe(III)-based ion pairs as stronger Lewis acid catalysts. This new catalytic system enables selective access to ()-olefins as carbonyl-olefin metathesis products. Mechanistic investigations suggest the regioselective formation and stereospecific fragmentation of intermediate oxetanes to be the origin of this selectivity. The optimized conditions are general for a variety of aryl aldehydes and trisubstituted olefins and are demonstrated for 28 examples in up to 64% overall yield.
本文描述了一种分子间羰基-烯烃复分解反应,该反应依赖基于超强亲电铁(III)的离子对作为更强的路易斯酸催化剂。这种新的催化体系能够选择性地获得()-烯烃作为羰基-烯烃复分解产物。机理研究表明,中间体氧杂环丁烷的区域选择性形成和立体专一性断裂是这种选择性的起源。优化后的条件适用于多种芳基醛和三取代烯烃,28个实例证明其总收率高达64%。