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C-H Bond Functionalization via Catalytic Migrative Cross-Coupling

Research Project
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01.04.2016
 - 31.03.2019

This proposal is dedicated to the development of a new C-H functionalization strategy allowing to selectively create a C-C bond at the terminal position of an alkane fragment. This strategy is based on the ability of group 10 metals to migrate along an alkyl chain via the ß-H elimination/p-complex rotation/insertion mechanism and undergo reductive elimination at the least substituted terminal position. This proposal features 3 Work Packages (WP) of progressively more challenging character. In WP1, the palladium(0)-catalyzed ligand-controlled regioconvergent coupling of organozinc compounds, obtained from mixtures of alkyl bromides, is proposed. Coupling this migrative cross-coupling with an initial C-H bromination step would allow to selectively functionalize alkanes in two-steps at the terminal carbon. WP2 features the development of a nickel-catalyzed version of the preceding migrative coupling, which would offer a useful complementarity both in terms of scope and mechanism. The main purpose of WP3 is to replace organozinc reagents employed in the Ni-catalyzed process (WP2) with photoredox-generated radicals, such as those generated from carboxylic acids or amines in combination with an Ir-based photocatalyst. This modification would allow to significantly expand the scope and practicability of this C-H functionalization strategy.

Funding

C-H Bond Functionalization via Catalytic Migrative Cross-Coupling

SNF Projekt (GrantsTool), 04.2016-03.2019 (36)
PI : Baudoin, Olivier.

Publications

Dupuy, Stéphanie et al. (2016) ‘Terminal-Selective Functionalization of Alkyl Chains by Regioconvergent Cross-Coupling’, Angewandte Chemie International Edition, 55(47), pp. 14793–14797. Available at: https://doi.org/10.1002/anie.201608535.

URLs
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Members (1)

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Olivier Baudoin

Principal Investigator