Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source

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Abstract: An enantioselective reduction of simple carbenium ions with cyclohexadienes containing a hydridic C−H bond at an asymmetrically substituted carbon atom is disclosed. The net reaction is a transfer hydrogenation of alkenes (styrenes) only employing chiral cyclohexadienes as dihydrogen surrogates. The trityl cation is used to initiate a Brønsted acid‐promoted process, in which a delicate intermolecular capture of a carbenium‐ion intermediate by the aforementioned chiral hydride source is enantioselectivity determining. Exclusively non‐covalent interactions are rendering one of the transition states energetically more favored, giving the reduction products in good enantiomeric ratios. The computed reaction mechanism supports the present findings as well as previous results obtained from studies on other transfer‐hydrogenation methods involving the cyclohexadiene platform.

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Bibliographic citation: Discrimination of the Enantiotopic Faces of Structurally Unbiased Carbenium Ions Employing a Cyclohexadiene‐Based Chiral Hydride Source ; day:14 ; month:06 ; year:2023 ; extent:7
Angewandte Chemie / International edition. International edition ; (14.06.2023) (gesamt 7)

Creator: Wolff, Benedikt
Qu, Zheng‐Wang
Grimme, Stefan
Oestreich, Martin

DOI: 10.1002/anie.202305295

URN: urn:nbn:de:101:1-2023061515152858538879

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

Last update: 14.08.2025, 10:47 AM CEST

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