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The First Crystal Structure of a Reactive Dirhodium Carbene Complex and a Versatile Method for the Preparation of Gold Carbenes by Rhodium‐to‐Gold Transmetalation
Author(s) -
Werlé Christophe,
Goddard Richard,
Fürstner Alois
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201506902
Subject(s) - carbene , transmetalation , rhodium , diazomethane , chemistry , phosphine , reactivity (psychology) , reactive intermediate , catalysis , combinatorial chemistry , organic chemistry , medicine , alternative medicine , pathology
Abstract The dirhodium carbene derived from bis(4‐methoxyphenyl)diazomethane and [Rh(tpa) 4 ]⋅CH 2 Cl 2 (tpa=triphenylacetate) was characterized by UV, IR, and NMR spectroscopy, HRMS, as well as by X‐ray diffraction. The isolated complex exhibits prototypical rhodium carbene reactivity in that it cyclopropanates 4‐methoxystyrene at low temperature. Experimental structural information on this important type of reactive intermediate is extremely scarce and thus serves as a reference point for mechanistic discussions of rhodium catalysis in general. Moreover, dirhodium carbenes are shown to undergo remarkably facile carbene transfer on treatment with [LAuNTf 2 ] (L=phosphine). This formal transmetalation opens a valuable new entry into gold carbene complexes that cannot easily be made otherwise; three fully characterized representatives illustrate this aspect.