Engel Douglas A, Dudley Gregory B
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL 32306-4390, USA.
Org Lett. 2006 Aug 31;8(18):4027-9. doi: 10.1021/ol0616743.
An atom-economical and efficient olefination strategy for ketones is described. Ethoxyacetylide addition followed by a gold-catalyzed Meyer-Schuster rearrangement affords alpha,beta-unsaturated esters, generally in excellent overall yield from the starting ketones. The alkynophilicity of Au3+ promotes an interaction with the electron-rich acetylenes that catalyzes the Meyer-Schuster rearrangement selectively over other conceivable pathways.
本文描述了一种用于酮的原子经济且高效的烯化策略。乙氧基乙炔加成后，再经金催化的迈耶-舒斯特重排反应可得到α,β-不饱和酯，通常从起始酮出发能获得优异的总产率。Au3+的亲炔性促进了其与富电子乙炔的相互作用，从而选择性地催化迈耶-舒斯特重排反应，而不是其他可能的途径。
