کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1314143 975947 2011 12 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Copper mediated defluorinative allylic alkylation of difluorohomoallyl alcohol derivatives directed to an efficient synthetic method for (Z)-fluoroalkene dipeptide isosteres
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Copper mediated defluorinative allylic alkylation of difluorohomoallyl alcohol derivatives directed to an efficient synthetic method for (Z)-fluoroalkene dipeptide isosteres
چکیده انگلیسی

Difluoroallylation of optically pure O-silylated (S)-2-methyl-3-hydroxypropanal 10a with bromodifluoropropene mediated by indium provided the corresponding difluorohomoallyl alcohol 11a with low diastereoselectivity, but without a decrease in optical purity. Defluorinative allylic alkylation of each diastereomer of the difluorohomoallyl alcohol efficiently proceeded by the reaction with trialkylaluminium and Cu(I) system or Grignard reagent and a catalytic amount of CuI system in THF to give the fluorine-substituted allylic alcohol 12 in an high yield and in an excellent Z selective manner. Subsequent imidate Claisen rearrangement of the allylic alcohol 12 proceeded with a complete 1,3-chirality transfer to give the fluoroalkene dipeptide isostere structure 14 after the final conversion of the primary alcohol 20 into the carboxylic acid form.

Figure optionsDownload as PowerPoint slideHighlights
► High yield and highly Z selective allylic alkylation reaction of difluorohomoally alcohol derivatives with Grignard reagents and CuI catalyst leading to fluoroallyl alcohol derivatives.
► Complete 1,3-chirality transfer in the imidate Claisen rearrangement of the above fluoroallyl alcohol derivatives.
► A convienient method for the preparation of (Z)-fluoroalkene dipeptide isosteres in optically pure form.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Fluorine Chemistry - Volume 132, Issue 5, May 2011, Pages 327–338
نویسندگان
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