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Phosphine-catalyzed remote α-C–H bond activation of alcohols or amines triggered by the radical trifluoromethylation of alkenes: reaction development and mechanistic insights

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Abstract

Intramolecular hydrogen atom transfer (HAT) for the remote functionalization of C(sp3)–H bonds has emerged as a powerful strategy, but its asymmetric diversification remains a great challenge because of the requirement of harsh reaction conditions and less enantiotopic discrimination. To overcome this, we described a general and efficient radical protocol for the concomitant functionalization of both alkenes and the remote α-C–H bonds of alcohols or amines via 1,5(6,7)-HAT triggered by the addition of a trifluoromethyl radical to alkenes in a highly controlled site-selective manner. Furthermore, such an approach could be developed for late-stage asymmetric diversification at the remote sp3-hydridized positions of alcohols or amines via a cascade sequence for the facile construction of chiral CF3-containing homoallylic alcohols or secondary amines with good to excellent enantioselectivities. Mechanistic experiments and DFT calculations revealed that 1,5(6,7)-HAT is a kinetically relevant process and provided a rationale for the observed different reactivities between the linear alkenyl alcohol or amine and alkenyl ketone or amide.

Graphical abstract: Phosphine-catalyzed remote α-C–H bond activation of alcohols or amines triggered by the radical trifluoromethylation of alkenes: reaction development and mechanistic insights

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Publication details

The article was received on 22 Jun 2017, accepted on 19 Jul 2017 and first published on 20 Jul 2017


Article type: Research Article
DOI: 10.1039/C7QO00500H
Citation: Org. Chem. Front., 2017, Advance Article
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    Phosphine-catalyzed remote α-C–H bond activation of alcohols or amines triggered by the radical trifluoromethylation of alkenes: reaction development and mechanistic insights

    L. Li, L. Ye, S. Ni, Z. Li, S. Chen, Y. Du, X. Li, L. Dang and X. Liu, Org. Chem. Front., 2017, Advance Article , DOI: 10.1039/C7QO00500H

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