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Synlett 2006(18): 2921-2928  
DOI: 10.1055/s-2006-951516
LETTER
© Georg Thieme Verlag Stuttgart · New York

Reduction of Allylpalladium(II)chloride Dimer by Formation of Allyloxy­silanes

Scott E. Denmark*, Russell C. Smith
245 Roger Adams Laboratory, Box 18, Department of Chemistry, University of Illinois, 600 S. Mathews Avenue, Urbana, IL 61801, USA
Fax: +1(217)3333984; e-Mail: denmark@scs.uiuc.edu;
Further Information

Publication History

Received 16 May 2006
Publication Date:
25 October 2006 (online)

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Abstract

The reduction of allylpalladium(II)chloride dimer (APC) to a Pd(0) species can be effected by reaction with alkali metal silanolates. The reduction is extremely rapid in the presence of chelating bisphosphine ligands and for a variety of silanolates.

Key words

palladium - silanolate - cross-coupling - reduction - mechanism

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17

Denmark, S. E.; Ober, M. H., unpublished results.

20

The presence of the disiloxane was confirmed by GC-MS analysis. This peak was the major constituent in the GC chromatogram as determined by relative area percents.

22

The stability of the silanolate was tested using 1H NMR spectroscopy. The 1H NMR spectrum of a 0.075 M solution of K+ 1a - in CH2Cl2 was unchanged after standing at r.t. for 5 h.

29

Response Factor (R f ) calculated using: R f = (mmol of internal standard*area of x)/(mmol of x*area of internal standard).