Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China).
Angew Chem Int Ed Engl. 2014 Nov 17;53(47):12902-6. doi: 10.1002/anie.201409141. Epub 2014 Oct 27.
o-Carboryne can undergo α-CH bond insertion with tertiary amines, thus affording α-carboranylated amines in very good regioselectivity and isolated yields. In this process, the nucleophilic addition of tertiary amines to the multiple bond of o-carboryne generates a zwitterionic intermediate. An intramolecular proton transfer, followed by a nucleophilic attack leads to the formation of the final product. Thus, regioselectivity is highly dependent upon the acidity of α-CH proton of tertiary amines. This approach serves as an efficient methodology for the preparation of a series of 1-aminoalkyl-o-carboranes.
o-卡宾可以与叔胺发生 α-CH 键插入反应，从而以非常好的区域选择性和分离产率得到 α-卡硼基化的胺。在这个过程中，叔胺的亲核加成到 o-卡宾的多重键上生成两性离子中间体。随后发生分子内质子转移和亲核进攻，形成最终产物。因此，区域选择性高度依赖于叔胺的 α-CH 质子的酸性。这种方法是制备一系列 1-氨基烷基-o-卡硼烷的有效方法。
