Intramolecular C-H insertion reactions of boroxy Fischer carbene complexes.: Regio- and diastereoselective modification of terpenes

被引:27
作者
Barluenga, J
Rodríguez, F
Vadecard, J
Bendix, M
Fañanás, FJ
López-Ortiz, F
Rodríguez, MA
机构
[1] Univ Oviedo, Inst Univ Quim Organomet Enrique Moles, Unidad Asociada, CSIC, E-33071 Oviedo, Spain
[2] Univ Almeria, Dept Geometria Topol & Quim Organ, Fac Ciencias Expt, E-04120 Almeria, Spain
[3] Univ La Rioja, Dept Quim, E-26071 Logrono, Spain
关键词
D O I
10.1021/ja991161+
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
In-situ-generated dialkylboroxy and diaminoboroxy Fischer carbene complexes lead to oxaborolane or oxazaborolidine derivatives via an intramolecular C-II insertion reaction. Further oxidation of these intermediates yields 1,3-diol or 1,2-amino alcohol derivatives. Diastereoselectivities as high as 99% are reached when starting from boroxy Fischer carbene complexes derived from terpenes, which represents a regio- and diastereoselective modification of this type of natural product. The influence of the C-beta substituents relative to the boron atom on the reaction path is studied, and a mechanism is proposed after identification of an intermediate by NMR. In addition, theoretical calculations show the presence of a boron-metal interaction, which could result as key step to the C-H insertion reaction.
引用
收藏
页码:8776 / 8782
页数:7
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