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Chemoselective Union of Olefins, Organohalides and Redox-Active Esters Enables Regioselective Alkene Dialkylation

preprint
submitted on 20.10.2020, 02:35 and posted on 20.10.2020, 10:22 by Tao Yang, Yi Jiang, Yixin Luo, Yu Lan, Ming Joo Koh
Multicomponent catalytic processes that can generate multiple C(sp3)-C(sp3) bonds in a single step under mild conditions,particularly if the catalysts and substrates are inexpensive, are highly sought-after in chemistry research for complex molecule synthesis. Here, we disclose an efficient Ni-catalysed reductive protocol that chemoselectively merges alkenyl amides with two different
aliphatic electrophiles. Starting materials are readily accessible from stable and abundant feedstock and products are furnished in up to >98:2 regioisomeric ratios. The present strategy eliminates the use of sensitive organometallic reagents, tolerates a wide array of complex functionalities and enables regiodivergent addition of two primary alkyl groups bearing similar electronic and steric attributes across aliphatic C=C bonds with exquisite control of site selectivity. Utility is underscored by the concise synthesis of bioactive compounds and post-reaction functionalizations leading to structurally diverse scaffolds. DFT studies revealed that the regiochemical outcome originates from the orthogonal reactivity and chemoselectivity profiles of in situ-generated organonickel species.

Funding

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

111 Project: D20003

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

The authors declare no competing financial interests.

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