Rhodium(II)-Catalyzed Hinsberg Dearomatization Using Trimethylsilyldiazomethane

Rhodium(II)-Catalyzed Hinsberg Dearomatization Using Trimethylsilyldiazomethane

Rhodium­(II) catalyzes carbene transfer from trimethylsilyldiazomethane to arylmethyl thioethers, generating sulfonium ylides that undergo [2,3]-sigmatropic rearrangement, punching quaternary centers into aromatic rings. The reaction works well with naphthalene, indole, and benzofuran ring systems,...

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Veröffentlicht in:Organic letters 2023-11, Vol.25 (45), p.8083-8088
Hauptverfasser: Combs, Jason R., Carter, David S., Gu, Fengyi, Jin, Xiaokang, Martin, Connor M., Resendiz, Elizabeth S., Van Vranken, David L.
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container_end_page 8088
container_issue 45
container_start_page 8083
container_title Organic letters
container_volume 25
creator Combs, Jason R.
Carter, David S.
Gu, Fengyi
Jin, Xiaokang
Martin, Connor M.
Resendiz, Elizabeth S.
Van Vranken, David L.
description Rhodium­(II) catalyzes carbene transfer from trimethylsilyldiazomethane to arylmethyl thioethers, generating sulfonium ylides that undergo [2,3]-sigmatropic rearrangement, punching quaternary centers into aromatic rings. The reaction works well with naphthalene, indole, and benzofuran ring systems, but the reaction is unsuccessful with the monocyclic benzene homologue. For aryl thioethers, Rh2(OAc)4 gives good results. For alkyl thioethers, the yields improve with Rh2(cap)4. Surprisingly, thioesters and thiocarbamates are also competent substrates for the reaction.
doi_str_mv 10.1021/acs.orglett.3c03130
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title Rhodium(II)-Catalyzed Hinsberg Dearomatization Using Trimethylsilyldiazomethane
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