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Nitrosoallene-Mediated endo-Cyclizations for the Synthesis of (Hetero)cyclic α-Substituted exo-Unsaturated Oximes
The Journal of Organic Chemistry ( IF 3.6 ) Pub Date : 2018-01-16 00:00:00 , DOI: 10.1021/acs.joc.7b02936
Hiroki Tanimoto 1 , Sho Ueda 1 , Tsumoru Morimoto 1 , Kiyomi Kakiuchi 1
Affiliation  

Nitrosoallene-mediated endo-dig cyclization reactions producing (hetero)cyclic exo-unsaturated oximes (enoximes) are described. The intramolecular 1,4-type addition to in situ generated nitrosoallenes afforded α-substituted cyclic enoximes with exo-methylene units, which are the favored conformation for further cyclizations. The strong electron-withdrawing ability of the nitroso group facilitated the construction of five-to-seven-membered ring systems via C–O, C–N, C–S, and C–C bond formations, including a quaternary carbon center, at low temperatures.

中文翻译:

Nitrosoallene介导的用于合成(杂)环状-Cyclizationsα取代型外切不饱和肟

描述了亚硝基亚砜介导的-dig环化反应,其产生(杂)环外-不饱和肟(烯肟)。分子内的1,4-型加成到原位生成的亚硝基亚芳基得到具有亚甲基单元的α-取代的环烯,这是用于进一步环化的有利构象。亚硝基的强大的吸电子能力通过C–O,C–N,C–S和C–C键的形成(包括一个季碳中心)促进了五至七元环系统的构建。低温。
更新日期:2018-01-16
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