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Synlett 2009(15): 2375-2381  
DOI: 10.1055/s-0029-1217739
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Celebrating 20 Years of SYNLETT - Special Essay: General Procedure for the Palladium-Catalyzed Selective Hydrophosphorylation of Alkynes

Valentine P. Ananikov*a, Levon L. Khemchyana, Irina P. Beletskaya*b
a Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect 47, Moscow 119991, Russian Federation
Fax: +7(499)1355328; e-Mail: val@ioc.ac.ru;
b Chemistry Department, Lomonosov Moscow State University, Vorob’evy gory, Moscow 119899, Russian Federation
Fax: +7(495)9393618; e-Mail: beletska@org.chem.msu.ru;
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Publication History

Received 8 May 2009
Publication Date:
27 August 2009 (online)

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Abstract

A novel catalytic system has been developed to accomplish the hydrophosphorylation of terminal and internal alkynes with high isolated yields (up to 96%) and excellent regio- and stereo­selectivity (>99:1). The key factor was to apply a low-ligated palladium/triphenylphosphane (1:2) catalytic system in the presence of a catalytic amount of trifluoroacetic acid. The catalytic system so developed has been applied successfully to permit the formation of diverse alkenylphosphonates utilizing a variety of available H-phos­phonates and alkynes.

Key words

addition reactions - alkynes - palladium - homogenous catalysis - phosphorylations

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12

The use of this compound to reverse the regioselectivity of a palladium-catalyzed reaction between diphenylphosphane oxide and alkynes was first reported in 1998, see ref. 9c. Later, Han et al. indicated that ‘it does not affect other palladium- or rhodium-catalyzed phosphoryl-hydrogen bond additions’, see ref. 9b; however, this additive was necessary to control the direction of phosphoryl-hydrogen addition in the case of the nickel system. Tanaka et al. have questioned the potential application of this additive for practical implementation in a recent study, see ref. 16. An acceptable mechanistic picture describing the influence of this additive on the regioselectivity of the addition reaction is not available thus far.

17

The ‘activated’ nature of the cyclic H-phosphonate facilitated the preferred formation of double addition product 7 in the palladium-catalyzed reaction, rather than the formation of product 3, e.g. see ref. 11.

18

See Supporting Information for a detailed description.

21

Compound Isolation and Purification: After completion of the reaction, the products were purified by dry-column flash chromatography on silica gel, see ref. 23. Hexane-EtOAc (for 3a-c, 3e-i, 4a, and 10) and hexane-EtOAc-EtOH (for 3d) gradient elution was applied. After drying in a vacuum, the pure products were obtained. The products were isolated as colorless or light-yellow oils, and their isolated yields given in Tables  [4] and  [5] were calculated based on the initial amount of the corresponding H-phosphonate.

22

Complete characterization of all the isolated products with ¹H, ¹³C, and ³¹P NMR spectroscopy, mass spectrometry, and microanalysis is provided in Section 6 of the Supporting Information.