Synfacts 2005(0): 0018-0018  
DOI: 10.1055/s-2005-865369
Synthesis of Heterocycles
© Georg Thieme Verlag Stuttgart · New York

Synthesis of 1-Phosphabarrelene Phosphine Sulfide Substituted Palladium(II) Complexes

Contributor(s): Victor Snieckus, Oleg M. Demchuk
O. Piechaczyk, M. Doux, L. Ricard, P. le Floch*
Ecole Polytechnique, Palaiseau, France
Synthesis of 1-Phosphabarrelene Phosphine Sulfide Substituted Palladium(II) Complexes: Application in the Catalyzed Suzuki Cross-Coupling Process in the Allylation of Secondary Amines
Organometallics  2005,  24:  1204-1213  
Further Information

Publication History

Publication Date:
20 July 2005 (online)


Significance

A general Diels-Alder-based synthesis of 1-phosphabarrelenes from substituted phosphinines is reported. Palladium complexes have been prepared which serve as good ligands for cross-coupling reactions and in the allylation of secondary amines with TON up to 7 × 106. X-ray crystal structural analysis and computational data of the complexes are presented.

Comment

The phosphabarrelenes, P-analogues of the classical barrelene (H. E. Zimmerman, R. M. Paufler J. Am. Chem. Soc. 1960, 82, 1514-1515) represent a unusual class of heterocycles and phosphorus ligands, which have received little attention (B. Breit, E. Fuchs Chem. Commun. 2004, 694-695). Aside from interest in its chemical reactivity, the three-dimensional heterocyclic core opens new horizons for rational ligand design not only for conventional Pd-catalyzed cross-coupling reactions but also for asymmetric catalytic processes.