Rh(I)催化烯醇酯的环羰化反应制备乙酰氧基 4-烷基-4-烯基环戊-3-烯-2-酮。
Rh(I)-catalyzed cyclocarbonylation of allenol esters to prepare acetoxy 4-alkylidenecyclopent-3-en-2-ones.
机构信息
Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA.
出版信息
J Org Chem. 2009 Nov 6;74(21):8314-20. doi: 10.1021/jo901459t.
Abstract
A Rh(I)-catalyzed cyclocarbonylation reaction of allenol esters has been examined and its synthetic viability established for the conversion of trisubstituted allenes to bicyclo[4.3.0] and -[5.3.0] skeletons possessing an alpha-acetoxy cyclopentadienone. Tetrasubstituted allenol acetates gave elimination products, providing examples of a cyclocarbonylation reaction between an alkyne and a latent cumulene or cumulene equivalent. Cleavage of the acetate affords a free hydroxyl group illustrating the utility of this method for accessing alpha-hydroxy carbonyls from allenol esters.
摘要
已考察了 Rh(I)催化的烯醇酯的环羰化反应，并确定了其合成可行性，可将三取代的烯丙醇转化为具有α-乙酰氧基环戊二烯酮的双环[4.3.0]和-[5.3.0]骨架。四取代的烯醇乙酸酯生成消除产物，为在炔烃和潜在的累积二烯或累积二烯等价物之间进行环羰化反应提供了实例。乙酸盐的裂解提供了游离的羟基，说明了该方法从烯醇酯中获得α-羟基羰基的用途。
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