α,β-Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5-Alkoxy Migration of 1,6-Enynes: Mechanisms and Applications.

α,β-Unsaturated Gold(I) Carbenes by Tandem Cyclization and 1,5-Alkoxy Migration of 1,6-Enynes: Mechanisms and Applications.
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DOI:
10.1002/chem.201602347
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发表时间:
2016-09-12
影响因子:
4.3
通讯作者:
Echavarren, Antonio M.
Echavarren, Antonio M.
中科院分区:
化学2区
文献类型:
--
作者:
Calleja, Pilar;Pablo, Oscar;Ranieri, Beatrice;Gaydou, Morgane;Pitaval, Anthony;Moreno, Maria;Raducan, Mihai;Echavarren, Antonio M.

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在炔丙基位置带有OR基团的1,6-烯炔生成α,β-不饱和的金(I)-卡宾/金(I)稳定的烯丙基阳离子,其可以被烯烃捕获以形成环丙烷或1,3-二酮,得到α-烷基化产物。最好的迁移基团是对硝基苯基醚,这导致相应的产物没有外消旋化。因此,改进的形式合成(+)-schisanwilsonene A已经完成。不同的竞争性反应途径已划定计算。
1,6‐Enynes bearing OR groups at the propargyl position generate α,β‐unsaturated gold(I)‐carbenes/ gold(I) stabilized allyl cations that can be trapped by alkenes to form cyclopropanes or 1,3‐diketones to give products of α‐alkylation. The best migrating group is p‐nitrophenyl ether, which leads to the corresponding products without racemization. Thus, an improved formal synthesis of (+)‐schisanwilsonene A has been accomplished. The different competitive reaction pathways have been delineated computationally.
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