Since its advent two decades ago, asymmetric organo/transition-metal combined catalysis (AOMC), including cooperative catalysis and relay catalysis, has leveraged redistribution of chemical bonds to build up molecular complexity and enantio-differentiation to form individual enantiomers with activations from versatile organocatalysts and transition-metal complexes. The goal of this perspective is to provide readers with the fundamental attributes of AOMC─orthogonality, kinetics, mechanism, and selectivity─to understand how an organocatalyst and a transition-metal complex would collaborate to enable fruitful new reaction development and what are the intrinsic pathways of unproductive events, such as catalyst self-quenching. In closing, future opportunities of AOMC have been directed toward the prediction of effective catalyst combination, introducing enzyme catalysis, and a focus on transient radical intermediate, to animate this area in the years to come.
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Organo/Transition-Metal Combined Catalysis Rejuvenates Both in Asymmetric Synthesis.
J Am Chem Soc
February 2022
Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Since its advent two decades ago, asymmetric organo/transition-metal combined catalysis (AOMC), including cooperative catalysis and relay catalysis, has leveraged redistribution of chemical bonds to build up molecular complexity and enantio-differentiation to form individual enantiomers with activations from versatile organocatalysts and transition-metal complexes. The goal of this perspective is to provide readers with the fundamental attributes of AOMC─orthogonality, kinetics, mechanism, and selectivity─to understand how an organocatalyst and a transition-metal complex would collaborate to enable fruitful new reaction development and what are the intrinsic pathways of unproductive events, such as catalyst self-quenching. In closing, future opportunities of AOMC have been directed toward the prediction of effective catalyst combination, introducing enzyme catalysis, and a focus on transient radical intermediate, to animate this area in the years to come.
View Article and Find Full Text PDFAsymmetric Organocatalysis Combined with Palladium Catalysis: Synergistic Effect on Enantioselective Mannich/α-Allylation Sequential Reactions of Pyrazolones in Constructing Vicinal Quaternary Stereocenters.
Org Lett
October 2019
Key Laboratory of Oil & Gas Fine Chemicals, Ministry of Education & Xinjiang Uyghur Autonomous Region, College of Chemistry and Chemical Engineering , Xinjiang University, Urumqi , Xinjiang 830000 , China.
In this letter, an efficient one-pot asymmetric sequential reaction is achieved by organo/transition metal relay catalysis in constructing two consecutive C-C bonds, which involves enantioselective amino squaramide catalytic Mannich-type addition of pyrazolones to isatin-derived ketimines and a subsequent palladium catalyzed diastereoselective allylic alkylation of pyrazolones with allylic acetates. An array of novel pyrazolone-aminooxindole-propylene structural motifs are obtained in a high level of yield and with excellent enantio- and diastereoselectivity (up to 95% yield, >20:1 dr, >99% ee). This methodology features the formation of vicinal quarternary carbon-stereocenters, and the second all-carbon tetrasubstituted stereogenic center is induced by joint action of the achiral palladium catalysis and the chiral environment generated from the Mannich step.
View Article and Find Full Text PDFTheory and Modeling of Asymmetric Catalytic Reactions.
Acc Chem Res
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Department of Chemistry and Biochemistry, University of California, Los Angeles , Los Angeles, California 90095-1569, United States.
Modern density functional theory and powerful contemporary computers have made it possible to explore complex reactions of value in organic synthesis. We describe recent explorations of mechanisms and origins of stereoselectivities with density functional theory calculations. The specific functionals and basis sets that are routinely used in computational studies of stereoselectivities of organic and organometallic reactions in our group are described, followed by our recent studies that uncovered the origins of stereocontrol in reactions catalyzed by (1) vicinal diamines, including cinchona alkaloid-derived primary amines, (2) vicinal amidophosphines, and (3) organo-transition-metal complexes.
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