D2-Symmetric Dirhodium Catalyst Derived from a 1,2,2-Triarylcyclopropanecarboxylate Ligand: Design, Synthesis and Application
- 2 November 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 133 (47), 19198-19204
- https://doi.org/10.1021/ja2074104
Abstract
Dirhodium tetrakis-(R)-(1-(4-bromophenyl)-2,2-diphenylcyclopropanecarboxylate) (Rh2(R-BTPCP)4) was found to be an effective chiral catalyst for enantioselective reactions of aryl- and styryldiazoacetates. Highly enantioselective cyclopropanations, tandem cyclopropanation/Cope rearrangements and a combined C–H functionalization/Cope rearrangement were achieved using Rh2(R-BTPCP)4 as catalyst. The advantages of Rh2(R-BTPCP)4 include its ease of synthesis, its tolerance to the size of the ester group in the styryldiazoacetates, and its compatibility with dichloromethane as solvent. Computational studies suggest that the catalyst adopts a D2-symmetric arrangement, but when the carbenoid binds to the catalyst, two of the p-bromophenyl groups on the ligands rotate outward to make room for the carbenoid and the approach of the substrate to the carbenoid.Keywords
This publication has 46 references indexed in Scilit:
- Catalyst-Controlled Formal [4 + 3] Cycloaddition Applied to the Total Synthesis of (+)-Barekoxide and (−)-BarekolJournal of the American Chemical Society, 2010
- Solvent-free catalytic enantioselective C–C bond forming reactions with very high catalyst turnover numbersChemical Science, 2010
- First X‐ray Structure of a N‐Naphthaloyl‐Tethered Chiral Dirhodium(II) Complex: Structural Basis for Tether Substitution Improving Asymmetric Control in Olefin CyclopropanationChemistry – A European Journal, 2010
- Combined Experimental and Computational Studies of Heterobimetallic Bi−Rh Paddlewheel Carboxylates as Catalysts for Metal Carbenoid TransformationsThe Journal of Organic Chemistry, 2009
- Chiral Crown Conformation of Rh2(S-PTTL)4: Enantioselective Cyclopropanation with α-Alkyl-α-diazoestersJournal of the American Chemical Society, 2009
- 1-Naphthyl and 4-indolyl arylalkylamines as selective monoamine reuptake inhibitorsBioorganic & Medicinal Chemistry Letters, 2009
- High symmetry dirhodium(II) paddlewheel complexes as chiral catalystsCoordination Chemistry Reviews, 2008
- Combining Quantum Mechanics Methods with Molecular Mechanics Methods in ONIOMJournal of Chemical Theory and Computation, 2006
- Tandem Asymmetric Cyclopropanation/Cope Rearrangement. A Highly Diastereoselective and Enantioselective Method for the Construction of 1,4-CycloheptadienesJournal of the American Chemical Society, 1998
- Ab initio energy-adjusted pseudopotentials for elements of groups 13–17Molecular Physics, 1993