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Synthesis of Carborane-Functionalized Heterocycles: Dearomative [2 + 2] Cycloaddition and sp2 C–H Insertion Reaction

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Functionalization of Carborane via Carboryne Intermediates

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Abstract

This chapter focuses on reaction of o-carboryne with N-protected indoles. An unexpected dearomative [2 + 2] cycloaddition is observed in the case of N-TMS indoles producing o-carborane-fused indolines in excellent chemoselectivity and isolated yields. In addition to the [2 + 2] cycloadducts, carboranylindoles derived from formal insertion reaction are also obtained for N-aryl indoles in which the product ratio is dependent upon the nature of substituents on aryl rings. The formal insertion reaction is dominant in the reaction of N-alkyl indoles. These protocols offer general and efficient methods for the preparation of o-carborane-functionalized indoles and indolines as well as other heterocycles. The observed dearomative [2 + 2] cycloaddition also represents the first example for indoles to undergo such reaction in the absence of transition metals or without UV irradiation.

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  1. Department of Chemistry and State Key Laboratory of Synthetic Chemistry, The Chinese University of Hong Kong, Hong Kong, China

    Da Zhao

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Correspondence to Da Zhao .

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Zhao, D. (2016). Synthesis of Carborane-Functionalized Heterocycles: Dearomative [2 + 2] Cycloaddition and sp2 C–H Insertion Reaction. In: Functionalization of Carborane via Carboryne Intermediates. Springer Theses. Springer, Singapore. https://doi.org/10.1007/978-981-10-1569-4_3

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