Hammett 13C NMR and X-ray studies of π-allylpalladium phosphinooxazoline chiral ligand complexes

[Display omitted] The transmission of substituent effects across the palladium center to the allyl carbons is monitored by 13C NMR and X-ray crystallography as a way to probe electronic asymmetry in chiral ligand design. Based on their similar chemical shift trends and X-ray structures, the π-allylp...

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Bibliographic Details
Published in:Tetrahedron letters 2005-02, Vol.46 (9), p.1441-1445
Main Authors: Armstrong, Paul B., Bennett, Lisa M., Constantine, Ryan N., Fields, Jessica L., Jasinski, Jerry P., Staples, Richard J., Bunt, Richard C.
Format: Article
Language:English
Subjects:
Asymmetric catalysis
Hammett analysis
N,P-ligands
Palladium
π-Allyl complexes
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Summary:[Display omitted] The transmission of substituent effects across the palladium center to the allyl carbons is monitored by 13C NMR and X-ray crystallography as a way to probe electronic asymmetry in chiral ligand design. Based on their similar chemical shift trends and X-ray structures, the π-allylpalladium intermediates provide a good model for early transition state reactions, which are less sensitive to electronic perturbations. Hammett analysis supports an electronic basis for enantioselection that increases as the transition state becomes later.
ISSN:0040-4039
1873-3581
DOI:10.1016/j.tetlet.2005.01.032