Insertion into non-activated C(sp3)—H bonds: rapid construction of an added-value molecular diverse library



The selective functionalization of non-activated C(sp3)—H bonds within alkyl chains represents one of the major challenges in synthetic organic chemistry. 1-bromoalkynes, readily available from simple starting materials, may be transformed into a library of molecularly complex and diverse compounds by means of a well-defined intramolecular C(sp3)—H bond insertion reaction, using extremely simple reaction conditions. In addition, these compounds display a C—Br bond amenable for further functionalization. A preliminary mechanistic study supports a concerted [1,5]-H shift / C—C bond formation involving a gold-stabilized vinylcation-like transition state. The most salient feature of this methodology is the ability to functionalize in a predictable way non-activated C(sp3)—H bonds without any sort of electronic, geometric, or conformational bias.

Version notes

New main text document including DFT calculations and the corresponding discussion. New suplementary materials document including computational details. Updated authors list


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Supplementary material

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Experimental procedures, spectroscopic data and computational details
Experimental procedures for the synthesis of starting materials and final products. Full caracterization of staring materials and final products. KIE determination experiments. 13C isotope labelling experiments. X-ray structures. Computational study