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Dirhodium Complexes Heterochiral-at-the-Metal Centers: An Alternative Type of Paddlewheel Catalyst for Asymmetric Synthesis

Year: 2025

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide The prototype of an entirely new class of dirhodium paddlewheel complexes is disclosed, which is chiral at both inequivalent metal centers although it carries just three different achiral μ-bridging equatorial ligands. One of them is a carboxamidate, which ensures selective carbene formation at the Rh[O 3 N] face of the catalyst; moreover, the −NH group engages the ester carbonyl of the emerging rhodium carbene intermediate derived from α-stannylated α-diazoacetate in interligand hydrogen bonding, which is critically important for controlling the stereochemical course of the ensuing [2 + 1] cycloaddition. The new heterochiral catalyst furnished stannylated cyclopropane derivatives with excellent diastereo- and enantioselectivity; moreover, a cyclopropane with a quaternary trifluoromethylated stereocenter was obtained with an unprecedented level of asymmetric induction.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c03567

Authors: Matthias Peeters, Lorenzo Baldinelli, Sofia Lerda, Giovanni Bistoni, Alois Fürstner

Institutions: Max-Planck-Institut für Kohlenforschung, University of Perugia

Language: English

Topic: Cyclopropane Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Max-Planck-Gesellschaft, Università degli Studi di Perugia, Ministero dell'Università e della Ricerca