Synthesis of highly functionalized cyclohexenone rings: rhodium-catalyzed 1,3-acyloxy migration and subsequent [5+1] cycloaddition.
Synthesis of highly functionalized cyclohexenone rings: rhodium-catalyzed 1,3-acyloxy migration and subsequent [5+1] cycloaddition.
复制标题
DOI：
10.1002/anie.201006881
复制
发表时间：
2011-02-07
影响因子：
16.6
通讯作者：
Tang, Weiping
中科院分区：
文献类型：
--
作者：
Shu, Dongxu;Li, Xiaoxun;Zhang, Min;Robichaux, Patrick J.;Tang, Weiping
The Diels–Alder cycloaddition represents the most powerful technology for the preparation of substituted cyclohexenes and has proven to be extremely valuable in organic synthesis.[1] However, efficient syntheses of cyclohexenes having diverse substitutions, stereochemistry, and functionalities are still challenging and continue to stimulate the development of novel cycloaddition reactions.[2] We report herein a stereoselective synthesis of highly functionalized cyclohexenones from substituted cyclopropanes through a rhodium-catalyzed 1, 3-acyloxy migration and subsequent [5+ 1] cycloaddition. Given the well-documented strategies for the preparation of optically pure cyclopropanes,[3] this promises to be a versatile method for the synthesis of complex cyclohexenones from cyclopropanes.[4]We previously reported a synthesis of highly substituted cyclobutenes from cyclopropyl metal carbenes derived from transition metal catalyzed decomposition of diazo compounds.[5, 6] A more convenient and atom-economical [7] alternative for generating metal carbene intermediates would be the 1, 2-acyloxy migration of propargyl esters, which has been realized using AuI,[8] PtII,[9] RuII,[10] PdII,[11] and more recently RhI,[12] the reports of which appeared while we were conducting our investigation.[13] When we searched for reaction conditions to form the cyclopropyl metal carbene 3 through 1, 2-acyloxy migration, we isolated the highly functionalized cyclohexenone 7 when [{Rh (CO) 2Cl} 2] was employed as the catalyst (Scheme 1).
登录
查看更多内容
影响因子：
2.3
作者：
Dudnik AS;Schwier T;Gevorgyan V
通讯作者：
Gevorgyan V
影响因子：
2.3
作者：
Kobayashi, T;Koga, Y;Narasaka, K
通讯作者：
Narasaka, K
影响因子：
4.9
作者：
Brancour, Celia;Fukuyama, Takahide;Malacria, Max
通讯作者：
Malacria, Max
影响因子：
5.2
作者：
Buzas, A;Istrate, F;Gagosz, F
通讯作者：
Gagosz, F
影响因子：
5.2
作者：
Dudnik, Alexander S.;Schwier, Todd;Gevorgyan, Vladimir
通讯作者：
Gevorgyan, Vladimir