Synthesis of Phosphorus Ligands from Zirconium Reagents. A Useful Approach

Author(s): Maria Zablocka, Jean-Pierre Majoral.

Journal Name: Current Organic Chemistry

Volume 11 , Issue 1 , 2007

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Abstract:

The use of several zirconium reagents as the Schwartz reagent [Cp2ZrHCl]n, the dimethylzirconocene Cp2ZrMe2, the zirconocene [Cp2Zr], and the diphenylzirconocene Cp2ZrPh2 allows the synthesis of a variety of new linear and cyclic P-C and P-N ligands. 1,1 diphosphines can be prepared from unsaturated monophosphines. A useful methodology involving ring opening reactions permits the preparation of phosphinite-phosphine and bis-phosphinite ligands. N-functionalized imines and β-diimines substituted with phosphino groups are obtained from cyanophosphines or dinitriles. Carbozirconation of chlorophospha-imine leads to the unprecedented P-metalated iminophosphorane which presents a versatile reactivity towards electrophiles and small unsaturated molecules. Constraint three and four phosphorus cycles can be easily isolated using [Cp2M] (M = Zr or Ti). Interactions between benzynezirconocene and unsaturated phosphines afford numerous methods to prepare linear and cyclic phosphorus reagents. Enantiomerically pure iminophosphines can be synthetized from phosphinozirconocene complexes.

Keywords: substituted phospholane, phosphorus-zirconium salts, Schwartz reagent, metallocene transition complexes, 1,1-diphosphines

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Article Details

VOLUME: 11
ISSUE: 1
Year: 2007
Page: [49 - 60]
Pages: 12
DOI: 10.2174/138527207779316480

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