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![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions
Published on: March 20, 2014
Proximal and Remote Twofold Stereogenicity Enabled by Rhodium-Catalyzed and Phosphine-Directed Murai Reaction
Junwei Li1, Qiao Li1, Zeqin Zhao1
1Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
Abstract:
The insertion of arene C-H bonds to alkenes (the Murai reaction) has been established as a strategic protocol to access value-added aromatics, but the regioselectivity is predominantly to 1,2-selectivity. On the other hand, terminal alkenes may undergo remote functionalization via chain-walking that is predominantly initiated by an exogenous hydride source. It remains a daunting challenge to integrate asymmetric Murai reaction and olefin chain-walking to expand the boundary of this reaction in terms of regio- and stereoselectivity. Reported herein is rhodium-catalyzed Murai reaction between arenes bearing an ortho diarylphosphino directing group and two categories of amide-functionalized terminal alkenes. In the case of long-chained terminal olefin-amides, the hydroarylation gives branched products via rapid chain-walking of metal alkyl species to the chelation-stabilized β position, affording proximally disposed axial and central chirality with Markovnikov selectivity. The 1,2-hydroarylation of α-substituted acrylamides afforded distally disposed axial and central chirality with anti-Markovnikov selectivity. The coupling system proceeds with high enantioselectivity, excellent diastereoselectivity (>20:1 d.r.), and 100% atom-economy. The catalytic reactivity has been enabled by judicious choice of additives and a chiral phosphoramidite, which overrides the inhibitive effect of the coupled product. Selected products proved to be effective chiral ligands in metal-catalyzed asymmetric C-C coupling reactions.
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