Rh2(S-PTTL)3TPAa mixed-ligand dirhodium(ii) catalyst for enantioselective reactions of -alkyl--diazoestersElectronic supplementary information (ESI) available: Experimental and computational procedures; cif files and full characterization details are provided. CCDC reference number 860998. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c2sc01134d

• Main Authors: Boruta, David T, Dmitrenko, Olga, Yap, Glenn P. A, Fox, Joseph M
• Format: Article
• Language: English
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c2sc01134d

Herein we report the synthesis of the mixed-ligand paddlewheel complex tris[ N -phthaloyl-( S )- tert -leucinate](triphenylacetate)dirhodium( ii ), Rh 2 ( S -PTTL) 3 TPA, the structure of which bears similarity to the chiral crown complex Rh 2 ( S -PTTL) 4 . Rh 2 ( S -PTTL) 3 TPA engages substrate classes (aliphatic alkynes, silylacetylenes, -olefins) that are especially challenging in intermolecular reactions of -alkyl--diazoesters, and catalyzes enantioselective cyclopropanation, cyclopropenation, and indole CH functionalization with yields and enantioselectivities that are comparable or superior to Rh 2 ( S -PTTL) 4 . Mixing ligands on paddlewheel complexes offers a versatile handle for diversifying catalyst structure and reactivity. The results described herein illustrate how mixed-ligand catalysts can create new opportunities for the optimization of catalytic asymmetric processes. Mixing ligands on a paddlewheel complex improves the scope and enantioselectivity of transformations of -alkyl--diazoesters.