کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
5214436 1383197 2015 12 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Theoretical investigation of the reaction of dialkylzincs with α-alkoxycarbonyl radicals. Evaluation of α-bromoacrylates as radical acceptors in radical-polar crossover processes
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آلی
پیش نمایش صفحه اول مقاله
Theoretical investigation of the reaction of dialkylzincs with α-alkoxycarbonyl radicals. Evaluation of α-bromoacrylates as radical acceptors in radical-polar crossover processes
چکیده انگلیسی

The evaluation of ethyl α-bromoacrylate as radical acceptor in dialkylzinc radical-polar cascades addresses the question of the parameters controlling homolytic substitution at zinc by α-alcoxycarbonyl radicals. Under non-degassed medium ethyl α-bromoacrylate reacts with diethylzinc to give a bromocyclopropane. The reaction involves successively radical addition, SH2 at zinc, conjugate addition of the resulting enolate to the electrophilic substrate and ring closure. Theoretical calculations were performed to get a better insight into the detailed mechanism. They highlight the impact of zinc(II) chelation on the formal SH2 step. Additional experiments performed in the presence of other electrophiles-aldehydes and acylsilanes-are discussed.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Tetrahedron - Volume 71, Issue 47, 25 November 2015, Pages 8991-9002
نویسندگان
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