Asymmetric Radical and Anionic Cyclizations of Axially Chiral Carbamates
Asymmetric Radical and Anionic Cyclizations of Axially Chiral Carbamates
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DOI：
10.1021/ol802616u
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发表时间：
2009-01-01
期刊：
影响因子：
5.2
通讯作者：
Curran, Dennis P.
中科院分区：
文献类型：
--
作者：
Guthrie, David B.;Curran, Dennis P.
N-2，4-二甲基-6-碘苯基-N-烯丙基苯胺的标准BOC、ALLOC和CBZ衍生物是轴向手性的，可以很容易地拆分成外消旋势垒超过30千卡/摩尔的阿托品。拆分的轴向手性氨基甲酸酯经过自由基和阴离子环化反应，在取代的二氢吲哚产物中，手性从N-Ar轴转移到新的立体中心。产品的氨基甲酸酯基团很容易被去除。
Standard Boc, Alloc, and Cbz derivatives of N-2,4-dimethyl-6-iodophenyl-N-allyl anilines are axially chiral and can be readily resolved Into atropisomers whose racemization barriers exceed 30 kcal/mol. The resolved axially chiral carbamates undergo radical and anionic cyclizations with high levels of chirality transfer from the N-Ar axis to the new stereocenter in the substituted dihydroindole products. The carbamate groups of the products are readily removed.