Directed, Palladium(II)-Catalyzed Enantioselective anti-Carboboration of Alkenyl Carbonyl Compounds
A substrate-directed enantioselective anti-carboboration reaction of alkenes has been developed, wherein a carbon-based nucleophile and a boron moiety are installed across the C=C bond through a 5-membered palladacycle intermediate. A preliminary result also shows it is possible to extend this react...
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| Published in: | ACS catalysis Vol. 9; no. 4; p. 3260 |
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| Main Authors: | , , , |
| Format: | Journal Article |
| Language: | English |
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United States
05.04.2019
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| ISSN: | 2155-5435, 2155-5435 |
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| Abstract | A substrate-directed enantioselective anti-carboboration reaction of alkenes has been developed, wherein a carbon-based nucleophile and a boron moiety are installed across the C=C bond through a 5-membered palladacycle intermediate. A preliminary result also shows it is possible to extend this reaction to alkenes that are more distal from the directing group and react via a 6-membered palladacycle. The reaction is promoted by a palladium(II) catalyst and a monodentate oxazoline ligand. A range of enantioenriched secondary alkylboronate products were obtained with moderate to high enantioselectivity that could be further upgraded by recrystallization. This work represents an efficient method to synthesize versatile and valuable alkylboronate building blocks. Building on an earlier mechanistic proposal by Peng, He, and Chen, a revised model is proposed to account for the stereoconvergent nature of this transformation. |
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| AbstractList | A substrate-directed enantioselective anti-carboboration reaction of alkenes has been developed, wherein a carbon-based nucleophile and a boron moiety are installed across the C=C bond through a 5-membered palladacycle intermediate. A preliminary result also shows it is possible to extend this reaction to alkenes that are more distal from the directing group and react via a 6-membered palladacycle. The reaction is promoted by a palladium(II) catalyst and a monodentate oxazoline ligand. A range of enantioenriched secondary alkylboronate products were obtained with moderate to high enantioselectivity that could be further upgraded by recrystallization. This work represents an efficient method to synthesize versatile and valuable alkylboronate building blocks. Building on an earlier mechanistic proposal by Peng, He, and Chen, a revised model is proposed to account for the stereoconvergent nature of this transformation.A substrate-directed enantioselective anti-carboboration reaction of alkenes has been developed, wherein a carbon-based nucleophile and a boron moiety are installed across the C=C bond through a 5-membered palladacycle intermediate. A preliminary result also shows it is possible to extend this reaction to alkenes that are more distal from the directing group and react via a 6-membered palladacycle. The reaction is promoted by a palladium(II) catalyst and a monodentate oxazoline ligand. A range of enantioenriched secondary alkylboronate products were obtained with moderate to high enantioselectivity that could be further upgraded by recrystallization. This work represents an efficient method to synthesize versatile and valuable alkylboronate building blocks. Building on an earlier mechanistic proposal by Peng, He, and Chen, a revised model is proposed to account for the stereoconvergent nature of this transformation. A substrate-directed enantioselective anti-carboboration reaction of alkenes has been developed, wherein a carbon-based nucleophile and a boron moiety are installed across the C=C bond through a 5-membered palladacycle intermediate. A preliminary result also shows it is possible to extend this reaction to alkenes that are more distal from the directing group and react via a 6-membered palladacycle. The reaction is promoted by a palladium(II) catalyst and a monodentate oxazoline ligand. A range of enantioenriched secondary alkylboronate products were obtained with moderate to high enantioselectivity that could be further upgraded by recrystallization. This work represents an efficient method to synthesize versatile and valuable alkylboronate building blocks. Building on an earlier mechanistic proposal by Peng, He, and Chen, a revised model is proposed to account for the stereoconvergent nature of this transformation. |
| Author | Liu, Zhen Engle, Keary M Li, Xiaohan Zeng, Tian |
| Author_xml | – sequence: 1 givenname: Zhen surname: Liu fullname: Liu, Zhen organization: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States – sequence: 2 givenname: Xiaohan surname: Li fullname: Li, Xiaohan organization: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States – sequence: 3 givenname: Tian surname: Zeng fullname: Zeng, Tian organization: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States – sequence: 4 givenname: Keary M surname: Engle fullname: Engle, Keary M organization: Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States |
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