A Desilylative Approach to Alkyl Substituted C (1)‐Ammonium Enolates: Application in Enantioselective (2+2) Cycloadditions

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Abstract: The catalytic generation of C (1)‐ammonium enolates from the corresponding α‐silyl‐α‐alkyl substituted carboxylic acids using the isothiourea HyperBTM is reported. This desilylative approach grants access to α‐unsubstituted and α‐alkyl substituted C (1)‐ammonium enolates, which are typically difficult to access through traditional methods reliant upon deprotonation. The scope and limitations of this process is established in enantioselective [2+2]‐cycloaddition processes with perfluoroalkylketones (31 examples, up to 96 % yield and >99: 1 er), as well as selective [2+2]‐cycloaddition with trifluoromethyl enones (4 examples, up to 75 % yield and >99: 1 er). Preliminary mechanistic studies indicate this process proceeds through an initial kinetic resolution of an in situ prepared (±)‐α‐silyl‐α‐alkyl substituted anhydride, while the reaction process exhibits overall pseudo zero‐order kinetics.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: A Desilylative Approach to Alkyl Substituted C (1)‐Ammonium Enolates: Application in Enantioselective (2+2) Cycloadditions ; day:08 ; month:08 ; year:2022 ; extent:1
Angewandte Chemie ; (08.08.2022) (gesamt 1)

Creator: Wang, Yihong
Young, Claire M.
Liu, Honglei
Hartley, Will C.
Wienhold, Max
Cordes, David. B.
Slawin, Alexandra M. Z.
Smith, Andrew D.

DOI: 10.1002/ange.202208800

URN: urn:nbn:de:101:1-2022080915135636958956

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:37 AM CEST

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Associated

Wang, Yihong
Young, Claire M.
Liu, Honglei
Hartley, Will C.
Wienhold, Max
Cordes, David. B.
Slawin, Alexandra M. Z.
Smith, Andrew D.

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