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首页> 外文期刊>Organometallics >Theoretical investigation on the mechanisms of the PtCl2-mediated cycloisomerization of polyfunctionalized 1,6-enynes. 2. Propargylic carboxylates
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Theoretical investigation on the mechanisms of the PtCl2-mediated cycloisomerization of polyfunctionalized 1,6-enynes. 2. Propargylic carboxylates

机译：PtCl2介导的多官能化1,6-烯炔的环异构化机理的理论研究。 2.丙炔基羧酸盐

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摘要

The PtCl2-mediated cycloisomerization of hept-1-en-6-ynes functionalized at propargylic positions shows a high versatility and may afford different kinds of products. On the basis of a broad DFT computational study, mechanistic understandings of these processes are provided. The results suggest that these reactions could proceed through cyclopropyl platinum carbenes formed by endo or by exo cyclization routes. The role of the propargylic substituent and the additional alkene chain for dienyne precursors in the course of each type of cycloisomerization is discussed. Thus, although the metathesis process and formation of polycyclic adducts involves an initial 5-exo cyclopropanation path, a propargylic acyl group promotes the formation of bicyclic enol esters by an initial endo cyclopropanation, followed by [1,2]-acyl migration. This bulky propargylic group also inhibits other cycloisomerization reactions due to steric interactions, such as the Alder-ene process, and simultaneously allows an easy [1,2]-acyl migration by anchimeric assistance to yield bicyclic [n.1.0] enol esters.
机译：PtCl 2介导的在炔丙基位置官能化的hept-1-en-6-ynes的环异构化具有很高的通用性，可以提供不同种类的产品。在广泛的DFT计算研究的基础上，提供了对这些过程的机械理解。结果表明，这些反应可以通过由内环或外环化途径形成的环丙基羧甲基卡宾进行。讨论了炔丙基取代基和附加烯烃链对二烯炔前体在每种类型的环异构化过程中的作用。因此，尽管复分解过程和多环加合物的形成涉及初始的5-外环丙烷化路径，但是炔丙基酰基通过初始的内环丙烷化而促进双环烯醇酯的形成，随后是[1,2]-酰基迁移。该庞大的炔丙基基团还由于空间相互作用而抑制了其他的环异构化反应，例如Alder-ene工艺，并且同时通过嵌合助剂允许容易的[1,2]-酰基迁移，从而生成双环[n.1.0]烯醇酯。

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