从炔烃衍生物出发的有机合成方法学

研究了过渡金属催化的炔烃衍生物的异构化反应.从α,β-炔酮、2-炔酸酯和2-炔酸酰胺可以生成相应的(E,E)-共轭双烯酮、双烯酸酯和双烯酸酰胺.首次从2-炔醇异构化为相应的2-烯酮或2-烯醛.这一反应具有简单、高产率和立体选择性的优点.假设反应烯经过连二烯中间体,然后再异构化成产物,这一反应提供了方便而有潜在应用价值的方法以制备天然产物合成时的重要中间体.

A synthetic methodology from acetylenic derivatives

A review with 23 refs. The transition metal catalyzed isomerization reactions of acetylenic derivatives were studied. (E,E)-conjugated dienones, dienoic esters and dienoic amides were synthesized from corresponding a,b-ynones, 2-ynoic esters and 2-ynoic amides, resp. 2-Ynols were first isomerized to the corresponding 2-enones or 2-enals. The reactions can be accomplished simply, in high yield, and stereoselectively. It is proposed that allenic compounds are initially formed as the main intermediates and then isomerized further to the products. A convenient and potential useful methodol. is provided for the preparation of important intermediates in the synthesis of natural products.