Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Coordination Chemistry, and Application in Pd-Catalyzed Allylic Alkylation
Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Coordination Chemistry, and Application in Pd-Catalyzed Allylic Alkylation
Authors (7): C. F. Czauderna, A. G. Jarvis, F. J. L. Heutz, D. B. Cordes, A. M. Z. Slawin, J. I. van der Vlugt, P. C. J. Kamer
Themes: Environment
DOI: 10.1021/om5008055
Citations: 15
Pub type: article-journal
Pub year: 2015

Publisher: American Chemical Society (ACS)

Issue: 9

License:

Publication date(s): 2015/05/11 (print) 2015/04/30 (online)

Pages: 1608-1618

Volume: 34 Issue: 9

Journal: Organometallics

Link: https://pubs.acs.org/doi/pdf/10.1021/om5008055

URL: http://dx.doi.org/10.1021/Om5008055

A series of diphosphine ligands bearing ester- and ether-modified diphenylether backbones have been prepared. The introduction of carboxylic acid or ether auxiliaries in the ortho-positions relative to the diphenylphosphine groups was achieved via straightforward four-step synthetic protocols, prior to introduction of the phosphines. The electronic properties of these backbone-modified DPEPhos ligands were evaluated by probing the relevant carbonyl stretching frequencies (νCO) of Ni(CO)2(PP) species (PP = diphosphine) using IR spectroscopy and by determining the phosphorus–selenium coupling constant JSe–P of phosphine selenide derivatives using 31P{1H} NMR spectroscopy. Also, the X-ray structure for the bis(carbonyl)nickel(0) species with one of the ligands is reported. The [Pd(η3-allyl)(PP)] complexes were characterized by multinuclear NMR spectroscopy and applied in the asymmetric allylic alkylation of l,3-diphenyl-2-propenyl acetate and cyclohex-2-enyl acetate with dimethyl malonate in order to benchmark their catalytic potential. The enantioselectivity (ranging from 3 to 70%) was found to depend on the size of the chiral auxiliary introduced within the diphenyl ether backbone and its proximity to the phosphorus donor groups and hence to the active metal center.

Name Description Publised
om5008055_si_001.pdf Supl. data for Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Co... 2015
om5008055_si_002.cif Supl. data for Chiral Wide-Bite-Angle Diphosphine Ligands: Synthesis, Co... 2015
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