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

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.

addition reactions - alkynes - palladium - homogenous catalysis - phosphorylations

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<A NAME="RA54309ST-12">12</A>

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.

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<A NAME="RA54309ST-17">17</A>

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.

<A NAME="RA54309ST-18">18</A>

See Supporting Information for a detailed description.

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<A NAME="RA54309ST-20">20</A> Palladium-Catalyzed Hydrophosphorylation; General Procedure: Under argon, Pd₂(dba)₃ (31.1 mg, 3.0 × 10^-5 mol) and Ph₃P (31.5 mg, 1.2 × 10^-4 mol) were placed into a septum-sealed tube equipped with a magnetic stir bar, followed by the addition of THF (0.5 mL) through the septum, and the mixture was stirred for 3 min. When the color of the solution became brown, the H-phosphonate (1.0 × 10^-³ mol) and alkyne (1.0 × 10^-³ mol) were added to the mixture through the septum. Then, TFA (11.4 mg, 1.0 × 10^-4 mol) was added, and the tube was capped with a PTFE-sealed screw cap. The mixture was stirred at 50 ˚C (see Tables 4 and 5 for additional details relating to the ratio of the reagents or conditions). After completion of the reaction, the color of the solution remained brown or changed to light brown

<A NAME="RA54309ST-21">21</A>

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.

<A NAME="RA54309ST-22">22</A>

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.

<A NAME="RA54309ST-23">23</A> Harwood LM. Aldrichimica Acta  1985,  18:  25