Rh2(S-PTTL)3TPA—a mixed-ligand dirhodium(ii) catalyst for enantioselective reactions of α-alkyl-α-diazoesters

Herein we report the synthesis of the mixed ligand paddlewheel complex dirhodium(II) tris[ N -phthaloyl-( S )-tert-leucinate] triphenylacetate, 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 class...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2012-05, Vol.3 (5), p.1589-1593
Main Authors: Boruta, David T., Dmitrenko, Olga, Yap, Glenn P. A., Fox, Joseph M.
Format: Article
Language:English
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Summary:Herein we report the synthesis of the mixed ligand paddlewheel complex dirhodium(II) tris[ N -phthaloyl-( S )-tert-leucinate] triphenylacetate, 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, α-olefins) that are especially challenging in intermolecular reactions of α-alkyl-α-diazoesters, and catalyzes enantioselective cyclopropanation, cyclopropenation, and indole C-H 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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c2sc01134d