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Hydrogenative carbonyl olefin metathesis-Gandon:Bour.pdf (1.16 MB)
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Synthesis of Medium-Sized Carbocycles by Gallium-Catalyzed Tandem Carbonyl-Olefin Metathesis/Transfer Hydrogenation

preprint
revised on 26.07.2019 and posted on 26.07.2019 by Alexandre Djurovic, Marie Vayer, Zhilong Li, Régis Guillot, Jean Pierre Baltaze, Vincent Gandon, Christophe Bour
We report a catalytic tandem process involving a ring-closing carbonyl-olefin metathesis and a transfer hydrogenation. 1,4-Cyclohexadiene has been used as H2 surrogate to reduce the cyclic alkenes formed after the metathesis step. The same NHC-stabilized cationic gallium(III) complex, [IPr˙GaCl2][SbF6], performs the two steps with functional group tolerance. This reaction is stereoselective, leading either to 1,2-cisdisubstituted cyclopentanes or to a variety of cyclohexanes. DFT computations support an unexpected mechanism involving the activation of 1,4-cyclohexadiene by superelectrophilic gallium(III) dimers.

Funding

CNRS

Ministère de lʼEnseignement supérieur, de la Recherche et de lʼInnovation (MESRI, PhD follows to A. Djurovic and M. Vayer

Université Paris Sud

Chinese Scholarship Council (CSC, PhD fellow to Z. Li)

History

Email Address of Submitting Author

christophe.bour@u-psud.fr

Institution

Université Paris Sud

Country

France

ORCID For Submitting Author

0000-0001-6733-5284

Declaration of Conflict of Interest

no conflict of interest

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