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Cocatalysis: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

Simultaneous operation of two distinct catalytic cycles that jointly produce one product constitutes cocatalysis (dual or synergistic catalysis). Each catalyst activates a different substrate or a different elementary step; neither cycle alone is competent for the overall transformation under the same conditions. Photoredox/palladium cocatalysis for enantioselective allylic alkylation pairs a radical-generating photocatalyst with a chiral palladium π-allyl cycle [1]. Brønsted-acid promotion of rhodium-catalyzed asymmetric hydrogenation of N-unprotected indoles is a cocatalytic arrangement in which the acid and the metal complex share the catalytic workload [2]. Nickel/decatungstate cocatalysis for acylation of aryl halides and α-bromo acetates with aldehydes likewise assigns hydrogen-atom transfer and cross-coupling to two separate catalysts [3]. The term requires turnover of both species and a mechanistic interconnection (shared intermediate, sequential activation, or concerted dual activation). A ligand, solvent, or stoichiometric additive that is not regenerated is not a cocatalyst. Cocatalysis is therefore a systems-level description of how two catalytic manifolds are coupled, not a synonym for any single named reaction.

  • cocatalysis
  • dual catalysis
  • synergistic catalysis
  • photoredox

Carbon dioxide utilization in catalysis • Process Chemistry and Technology • Chemical Engineering • Physical Sciences

References

  1. Hong-Hao Zhang; Jia-Jia Zhao; Shouyun Yu; Enantioselective Allylic Alkylation with 4-Alkyl-1,4-dihydro-pyridines Enabled by Photoredox/Palladium Cocatalysis. J. Am. Chem. Soc. 2018, 140, 16914-16919, 10.1021/jacs.8b10766.
  2. Jialin Wen; Xiangru Fan; Renchang Tan; Hui-Chun Chien; Qinghai Zhou; Lung Wa Chung; Xumu Zhang; Brønsted-Acid-Promoted Rh-Catalyzed Asymmetric Hydrogenation of N-Unprotected Indoles: A Cocatalysis of Transition Metal and Anion Binding. Org. Lett. 2018, 20, 2143-2147, 10.1021/acs.orglett.8b00312.
  3. Pei Fan; Chang Zhang; Linchuan Zhang; Chuan Wang; Acylation of Aryl Halides and α-Bromo Acetates with Aldehydes Enabled by Nickel/TBADT Cocatalysis. Org. Lett. 2020, 22, 3875-3878, 10.1021/acs.orglett.0c01121.
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