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Alkyl Halides as Both Hydride and Alkyl Sources in Catalytic Regioselective Reductive Olefin Hydroalkylation

preprint
revised on 05.10.2020, 04:49 and posted on 05.10.2020, 13:01 by Xianxiao Chen, Weidong Rao, Tao Yang, Ming Joo Koh
Among the plethora of catalytic methods developed for hydrocarbofunctionalization of olefins to date, reactions that regioselectively install a functionalized alkyl unit at the 2-position of a terminal unactivated C=C bond to afford branched products are scarce. Here, we show that a Ni-based catalyst in conjunction with a stoichiometric reducing agent promote Markovnikov-selective hydroalkylation of unactivated alkenes tethered to a recyclable 8-aminoquinaldine directing auxiliary. These mild reductive processes employ readily available primary and secondary haloalkanes as both the hydride and alkyl donor, obviating the need for additional hydrosilane, acidic or basic additives. Reactions of alkenyl amides with ≥five-carbon chain length regioselectively afforded β-alkylated products through remote hydroalkylation, underscoring the fidelity of the catalytic process and the directing group's capability in stabilizing five-membered nickelacycle intermediates. The operationally simple protocol exhibits exceptional functional group tolerance and is amenable to the synthesis of bioactive molecules as well as regioconvergent transformations.

Funding

National University of Singapore Academic Research Fund Tier 1: R-143-000-A77-114

Project Funded by the National First-class Disciplines (PNFD)

Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)

History

Email Address of Submitting Author

chmkmj@nus.edu.sg

Institution

National University of Singapore

Country

Singapore

ORCID For Submitting Author

0000-0002-2534-4921

Declaration of Conflict of Interest

No conflict of interest

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