Volume 2020, Issue 46 p. 7131-7133
Communication

trans-Cyclooctenes as Chiral Ligands in Rhodium-Catalyzed Asymmetric 1,4-Additions

Tagui Nagano

Tagui Nagano

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan

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Shunsuke Einaru

Shunsuke Einaru

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan

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Kenta Shitamichi

Kenta Shitamichi

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan

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Dr. Keisuke Asano

Corresponding Author

Dr. Keisuke Asano

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, Kyoto 615-8510, Japan

E-mail: [email protected]

E-mail: [email protected]

https://smatsubara.wixsite.com/matsubara-kyoto-u/home

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Dr. Seijiro Matsubara

Corresponding Author

Dr. Seijiro Matsubara

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, 615-8510 Kyoto, Japan

Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyotodaigaku-katsura, Nishikyo, Kyoto 615-8510, Japan

E-mail: [email protected]

E-mail: [email protected]

https://smatsubara.wixsite.com/matsubara-kyoto-u/home

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First published: 26 August 2020
Citations: 6

Graphical Abstract

trans-Cyclooctenes serve as asymmetric ligands during the rhodium-catalyzed 1,4-additions of organotin reagents to enones. The potentials of these chiral olefins to provide efficient coordination spheres for asymmetric metal catalysis are demonstrated for the first time. These findings provide chiral frameworks for the design of asymmetric ligands for metal catalysts.

Abstract

trans-Cyclooctenes serve as asymmetric ligands for the rhodium-catalyzed 1,4-additions of organotin reagents to enones. We demonstrate, for the first time, that these chiral olefins can provide efficient coordination spheres for asymmetric metal catalysis. As the asymmetric environment around the reaction site is constructed by the trans-cyclooctene framework, the introduction of a substituent at the allylic position further improves enantioselectivity to 93 % ee. These findings provide new chiral framework designs for the asymmetric ligands of metal catalysts.