Research article summary (published 12 Oct 2009):

Optically active (aR)- and (aS)-linear and vaulted biaryl ligands: deracemization versus oxidative dimerization.

Full Abstract

The copper-mediated deracemization of the C2-symmetric vaulted biaryl ligands VANOL and VAPOL has been investigated. In the course of the studies that have led to a more reliable procedure for this process, an unprecedented oxidative dimerization of these ligands has been uncovered. The structures of these oxidative dimerization products were elucidated by a series of NMR experiments, and these assignments were supported by other spectroscopic techniques as well as their chemical reactivity. This oxidative dimerization process was not observed for the linear biaryl ligands BANOL and BINOL, although the new deracemization procedure was effective for the generation of BINOL with high optical purity. The (aS)-enantiomers of BINOL, VANOL and VAPOL were accessible with a copper complex of (-)-sparteine, and the (aR)-enantiomeric series were accessible with a copper complex of O'Brien's diamine. Both (-)-sparteine and O'Brien's diamine give higher optical purities with VANOL and VAPOL than with BINOL, and this is consistent with the steric congestion present in the matched and mismatched copper complexes of these diamines with the biaryl ligands.

Author information

Author/s: Hu, Gang (G); Holmes, Daniel (D); Gendhar, Brina Fay (BF); Wulff, William D (WD);

Affiliation: Department of Chemistry, Michigan State University, East Lansing, Michigan 48824, USA.

Grants: GM 63019 (Agency:NIGMS NIH HHS)

Journal and publication information

Publication Type: Journal Article; Research Support, N.I.H., Extramural

Journal: Journal of the American Chemical Society (J Am Chem Soc), published in United States. (Language: eng)

Reference: 2009-Oct; vol 131 (issue 40) : pp 14355-64

Dates: Created 2009/10/07; Completed 2009/11/13;

PMID: 19754056, status: MEDLINE (last retrieved date: 11/15/2009)

Sourced from the National Library of Medicine. Abstract text and other information may be subject to copyright.

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MeSH headings (categories)

This article was linked to the MeSH Headings (categories) shown below.

Alkynes - chemistry Copper - chemistry Dimerization Ligands Magnetic Resonance Spectroscopy - methods Naphthalenes - chemical synthesis; chemistry

Naphthalenes - chemical synthesis; chemistry Naphthols - chemical synthesis; chemistry Oxidation-Reduction Phenanthrenes - chemical synthesis; chemistry Sparteine - chemistry Stereoisomerism

Note: Bold headings indicate primary MeSH headings or qualifiers.

Associated Chemicals: Alkynes (0) ; BINOL, naphthol (0) ; Ligands (0) ; Naphthalenes (0) ; Naphthols (0) ; Phenanthrenes (0) ; VANOL ligand (0) ; VAPOL ligand (0) ; Copper (7440-50-8) ; Sparteine (90-39-1)

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