Nickel‐Catalyzed Allylic Alkylation with Diarylmethane Pronucleophiles: Reaction Development and Mechanistic Insights |
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| Authors: | Sheng‐Chun Sha Hui Jiang Jianyou Mao Ana Bellomo Soo A. Jeong Patrick J. Walsh |
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| Affiliation: | Roy and Diana Vagelos Laboratories, Penn/Merck Laboratory for High-Throughput Experimentation, Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA |
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| Abstract: | Palladium‐catalyzed allylic substitution reactions are among the most efficient methods to construct C?C bonds between sp3‐hybridized carbon atoms. In contrast, much less work has been done with nickel catalysts, perhaps because of the different mechanisms of the allylic substitution reactions. Palladium catalysts generally undergo substitution by a “soft”‐nucleophile pathway, wherein the nucleophile attacks the allyl group externally. Nickel catalysts are usually paired with “hard” nucleophiles, which attack the metal before C?C bond formation. Introduced herein is a rare nickel‐based catalyst which promotes substitution with diarylmethane pronucleophiles by the soft‐nucleophile pathway. Preliminary studies on the asymmetric allylic alkylation are promising. |
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| Keywords: | allylic compounds asymmetric catalysis cross-coupling nickel synthetic methods |
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