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. 2018 May 11;9(22):5074-5081.
doi: 10.1039/c8sc01595c. eCollection 2018 Jun 14.

Rhodium-catalyzed asymmetric hydroamination and hydroindolation of keto-vinylidenecyclopropanes

Song Yang  1 , Quan-Zhe Li  1 , Chen Xu  1 , Qin Xu  1 , Min Shi  1   2   3
Affiliations

Rhodium-catalyzed asymmetric hydroamination and hydroindolation of keto-vinylidenecyclopropanes

Song Yang et al. Chem Sci. .

Abstract

We reported a highly regio- and enantioselective hydroamination and hydroindolation of keto-vinylidenecyclopropanes via cationic Rh(i) catalysis in this context. The combination of various secondary amines and indoles with keto-vinylidenecyclopropanes afforded the corresponding hydrofunctionalization products in good to excellent yields with outstanding ee values under mild conditions. A new TMM-Rh model complex was proposed, providing an atom economical Rh-π-allyl precursor at the same time. Moreover, the resulting products could easily be transformed into more complex polyheterocycles upon further synthetic manipulation.

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Figures

Scheme 1
Scheme 1. Previous work and this work.
Scheme 2
Scheme 2. One-pot asymmetric N1 allylic alkylation of indoles.
Scheme 3
Scheme 3. Derivatizations of the products 3aa and 6aa.
Scheme 4
Scheme 4. A plausible reaction mechanism.
See this image and copyright information in PMC

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