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Reaction mechanism and chemoselectivity of gold(Ⅰ)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans 被引量:1

Reaction mechanism and chemoselectivity of gold(Ⅰ)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles to yield substituted furans
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摘要 The mechanisms of gold(I)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles have been investi- gated using density functional theory calculations at the B3LYP/6-31G (d, p) level of theory. A polarizable continuum model (PCM) has been established in order to evaluate the effects of solvents on the reactions. The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate. The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst. Furthermore, the regioselectivity and effect of substituents has been discussed, including an analysis of energy, bond length, and natural bond orbital (NBO) charge distributions in the rate-determining step. Our computational results are consistent with earlier experimental observations. The mechanisms of gold(Ⅰ)-catalyzed cycloaddition of 1-(1-alkynyl) cyclopropyl ketones with nucleophiles have been investigated using density functional theory calculations at the B3LYP/6-31G(d,p) level of theory.A polarizable continuum model(PCM) has been established in order to evaluate the effects of solvents on the reactions.The results of the calculations indicate that the first step of the catalytic cycle is the cyclization of the carbonyl oxygen onto the triple bond which forms a new and stable resonance structure of an oxonium ion and a carbocation intermediate.The subsequent ring expansion step results in the formation of the final product and regeneration of the catalyst.Furthermore,the regioselectivity and effect of substituents has been discussed,including an analysis of energy,bond length,and natural bond orbital(NBO) charge distributions in the rate-determining step.Our computational results are consistent with earlier experimental observations.
出处 《Science China Chemistry》 SCIE EI CAS 2012年第7期1413-1420,共8页 中国科学(化学英文版)
基金 supported by the Natural Science Foundation of Gansu Province (10710RJZA114)
关键词 substituted furans Au(l)-catalyzed regioselectivity substituent effects 催化循环 亲核试剂 环加成 化学选择性 反应机理 黄金 丙基 呋喃
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