Site- and Enantioselective Iridium-Catalyzed Desymmetric Mono-Hydrogenation of 1,4-Dienes

Wu H, Su H, Schulze E, Peters BBC, Nolan MD, Yang J, Singh T, Ahlquist MSG, Andersson PG (2021)

Publication Type: Journal article

Publication year: 2021

Journal

Angewandte Chemie International Edition Wiley

Book Volume: 60

Pages Range: 19428-19434

Journal Issue: 35

DOI: 10.1002/anie.202107267

Abstract

The control of site selectivity in asymmetric mono-hydrogenation of dienes or polyenes remains largely underdeveloped. Herein, we present a highly efficient desymmetrization of 1,4-dienes via iridium-catalyzed site- and enantioselective hydrogenation. This methodology demonstrates the first iridium-catalyzed hydrogenative desymmetriation of meso dienes and provides a concise approach to the installation of two vicinal stereogenic centers adjacent to an alkene. High isolated yields (up to 96 %) and excellent diastereo- and enantioselectivities (up to 99:1 d.r. and 99 % ee) were obtained for a series of divinyl carbinol and divinyl carbinamide substrates. DFT calculations reveal that an interaction between the hydroxy oxygen and the reacting hydride is responsible for the stereoselectivity of the desymmetrization of the divinyl carbinol. Based on the calculated energy profiles, a model that simulates product distribution over time was applied to show an intuitive kinetics of this process. The usefulness of the methodology was demonstrated by the synthesis of the key intermediates of natural products zaragozic acid A and (+)-invictolide.

Authors with CRIS profile

Erik Schulze

Involved external institutions

Stockholm University / Stockholms universitet SE Sweden (SE) University of KwaZulu-Natal (UKZN) ZA South Africa (ZA) Royal Institute of Technology / Kungliga Tekniska Högskolan (KTH) SE Sweden (SE)

How to cite

APA:

Wu, H., Su, H., Schulze, E., Peters, B.B.C., Nolan, M.D., Yang, J.,... Andersson, P.G. (2021). Site- and Enantioselective Iridium-Catalyzed Desymmetric Mono-Hydrogenation of 1,4-Dienes. Angewandte Chemie International Edition, 60(35), 19428-19434. https://dx.doi.org/10.1002/anie.202107267

MLA:

Wu, Haibo, et al. "Site- and Enantioselective Iridium-Catalyzed Desymmetric Mono-Hydrogenation of 1,4-Dienes." Angewandte Chemie International Edition 60.35 (2021): 19428-19434.

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