Highly stereoselective synthesis of homoallylic amines based on addition of allyltrichlorosilanes to benzoylhydrazones

被引:85
作者
Hirabayashi, R [1 ]
Ogawa, C [1 ]
Sugiura, M [1 ]
Kobayashi, S [1 ]
机构
[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Japan Sci & Technol Corp, CREST,Bunkyo Ku, Tokyo 1130033, Japan
关键词
D O I
10.1021/ja011125m
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Allyltrichlorosilanes reacted with benzoylhydrazones in DMF without the use of any catalyst to afford the corresponding homoallylic benzoylhydrazines in good to high yields. The reactions proceeded at 0 degreesC to room temperature under mild conditions. In addition, it was found that the reactions tolerated well the steric hindrance of hydrazones and allyltrichlorosilanes. Indeed, ketone-derived benzoylhydrazones reacted with allyltrichlorosilane smoothly to afford the corresponding N'-tert-alkyl-N-benzoylhydrazines in high yields. In crotylation with (E)- and (Z)-crotyltrichlorosilanes, syn- and anti-adducts were stereospecifically obtained, respectively. These reactions. are most likely to proceed via a cyclic chairlike transition state where the R group takes an axial position. When alpha -heteroatom-substituted chiral benzoylhydrazones were used, high anti-diastereoselectivities were observed. These adducts can be readily converted to homoallylic amines in high yields without epimerization.
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页码:9493 / 9499
页数:7
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