4.8 Article

Gold(I)-Catalyzed Benzylic C(sp3)-H Functionalizations: Divergent Synthesis of Indole[a]- and [b]-Fused Polycycles

Journal

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 62, Issue 3, Pages -

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202213653

Keywords

C-H Bond Functionalization; Carbenes; Fused Indoles; Gold Catalysis; Hydride Shift

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In this study, phenyl azides substituted by an (alkylphenyl)ethynyl group were found to facilitate benzylic sp(3)(C-H) functionalization under the presence of a JohnPhosAu catalyst, resulting in the synthesis of indole-fused tetra- and pentacycles through divergent N- or C-cyclization. The chemoselectivity of the reaction was found to be influenced by the counter-anion, the electron density of the alpha-imino gold(I) carbene, and the alkyl groups stabilizing the benzylic carbocation.
Phenyl azides substituted by an (alkylphenyl)ethynyl group facilitate benzylic sp(3)(C-H) functionalization in the presence of a JohnPhosAu catalyst, resulting in indole-fused tetra- and pentacycles via divergent N- or C-cyclization. The chemoselectivity is influenced depending on the counter-anion, the electron density of the alpha-imino gold(I) carbene, and the alkyl groups stabilizing the benzylic carbocation originating from a 1,5-hydride shift. An isotopic labeling experiment demonstrates the involvement of an indolylgold(I) species resulting from a tautomerization that is much faster than the deauration. The formation of a benzylic sp(3)(C-H) functionalization leading to an indole-fused seven-membered ring is also demonstrated.

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