Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles DOI

Hongxuan Zhai,

Kang Lv, Jiayan Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 29214 - 29223

Опубликована: Окт. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Язык: Английский

Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles DOI

Hongxuan Zhai,

Kang Lv, Jiayan Li

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(42), С. 29214 - 29223

Опубликована: Окт. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Язык: Английский

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