铑催化的3-酰氧基-1,4-烯炔与烯烃的立体选择性分子内[5+2]环加成反应
Rhodium-Catalyzed Stereoselective Intramolecular [5 + 2] Cycloaddition of 3-Acyloxy 1,4-Enyne and Alkene.
作者信息
Shu Xing-zhong, Schienebeck Casi M, Li Xiaoxun, Zhou Xin, Song Wangze, Chen Lianqing, Guzei Ilia A, Tang Weiping
机构信息
School of Pharmacy, University of Wisconsin-Madison , Madison, Wisconsin 53705, United States.
Department of Chemistry, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.
出版信息
Org Lett. 2015 Oct 16;17(20):5128-31. doi: 10.1021/acs.orglett.5b02665. Epub 2015 Oct 6.
Abstract
The first rhodium-catalyzed intramolecular [5 + 2] cycloaddition of 3-acyloxy 1,4-enyne and alkene was developed. The cycloaddition is highly diastereoselective in most cases. Various cis-fused bicyclo[5.3.0]decadienes were prepared stereoselectively. The chirality in the propargylic ester starting materials could be transferred to the bicyclic products with high efficiency. Electron-deficient phosphine ligand greatly facilitated the cycloaddition. Up to three new stereogenic centers could be generated. The resulting diene in the products could be hydrolyzed to enones, which allowed the introduction of more functional groups to the seven-membered ring.
摘要
首次实现了铑催化的3-酰氧基-1,4-烯炔与烯烃的分子内[5+2]环加成反应。在大多数情况下，该环加成反应具有高度的非对映选择性。立体选择性地制备了各种顺式稠合的双环[5.3.0]癸二烯。炔丙基酯起始原料中的手性能够高效地转移至双环产物中。缺电子膦配体极大地促进了环加成反应。最多可生成三个新的立体中心。产物中的二烯可水解为烯酮，这使得能够向七元环引入更多官能团。
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