Journal
JOURNAL OF ORGANOMETALLIC CHEMISTRY
Volume 696, Issue 20, Pages 3127-3134Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2011.05.015
Keywords
Carbene; diNHC; Chiral; C-2-symmetric; Rhodium; Enantioselective catalysis; Arylboronic acid
Categories
Funding
- NSF [CHE-0821346]
- UF
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This manuscript describes the synthesis and characterization of new derivatives of di-N-heterocyclic carbene (diNHC) ligands derived from trans-9,10-dihydro-9,10-ethanoanthracene-11,12-diylmethanediyl (DEAM) and trans-9,10-dihydro-9,10-ethanoanthracene-11,12-diyl (DEA). Synthesized as the diazolium salts, the new ligands are employed, in conjunction with known derivatives, to examine specific properties than influence the chiral induction in rhodium-catalyzed arylboronic acid addition to cyclohex-2enones. Three properties of the diNHC ligands are modified and include: 1) the size and composition of the N-heterocyclic substituent (Me, Pr-i, Bn, CHPh2, o-MeBn, and R-CHMePh), 2) the type of N-heterocycle (benzimidazole versus imidazole), and 3) the size of the chiral pocket (DEAM versus DEA). Results from the catalytic studies indicate the DEAM ligand, which contains an extra CH2 group compared to DEA, is too flexible to induce enantiomeric excess. The DEA derivatives containing an imidazole or benzimidazole provide distinctly different results despite relatively small differences between the heterocyclic carbene donors. An unexpected source of chiral induction is rationalized using results from catalytic data (% e.e.) and complemented by X-ray structural data and DFT calculations. Published by Elsevier B.V.
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