In the last 20 years N-heterocyclic carbenes (NHCs)1,2 and cyclic (alkyl)(amino)carbenes (CAACs)3 have revolutionized catalysis by helping with the stabilization of highly reactive intermediates. More recently, increasing numbers of multifunctional NHCs4 have found widespread application in catalysis and coordination chemistry. With respect to this, the synthesis of donor-functionalized CAACs derivatives has remained a challenging task. Recently, we discovered that cyclic enamine (1) reacts with various electrophiles, to afford a variety of donor-functionalized CAAC precursors (2-5). Deprotonation with KHMDS quantitatively afforded the corresponding free CAACs which were perfectly stable at room temperature, thus allowing straightforward coordination to a variety of metal centers. Studies with the Ph2P-functionalized CAAC showed that bidentate coordination can be obtained for Rh(I) and Pd(II), while dinuclear complexes are observed with Au(I) and Cu(I). Catalytic properties of these complexes will be also reported. 1. Herrmann, W. A. Angew. Chem. Int. Ed. 2002, 41, 1290. 2. Hahn, F. E.; Jahnke, M. C. Angew. Chem. Int. Ed. 2008, 47, 3122. 3. Soleilhavoup, M.; Bertrand, G. Acc. Chem. Res. 2015, 48, 256. 4. Kühl, O., Ed. Functionalized N-Heterocyclic Carbene Complexes; Wiley: Chichester, UK, 2010.

Donor-functionalized cyclic (alkyl)(amino)carbenes (CAACs): Synthesis, coordination, and catalysis

251st National Meeting (2016)

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