A Convenient and Direct Route to Phosphinoalkynes via Copper-Catalyzed Cross-Coupling of Terminal Alkynes with Chlorophosphanes

 

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Abstract

A new efficient method to obtain various alkynylphosphanes R_nP(-R′)_3-n [R = Ar, Alk, alkoxy, amido R′ = Ar, Het, Alk, CH₂Z (Z = OMe, NMe₂), n = 0-2] has been developed by means of cross-coupling reaction of chlorophosphanes R_nPCl_3-n (R = Ar, Alk, Alkoxy) with terminal alkynes catalyzed by cuprous salts.

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As found from X-ray data (Figure [1] ), the copper atom in the structure of (Ph₂PCl)₃CuI adopts a tetrahedral coordination. The copper and chlorine atoms are situated on either sides of the plane of phosphorus atoms. The Cu(1) atom is deviated from the plane of P(1), P(2) and P(3) atoms to 0.75 Å. Also, the chlorine atoms are antiperiplanar to the iodine atom, the torsion angle ClPCuI is equal to 167° on an average. X-ray investigation of structure 1 was carried out on Bruker Smart CCD 1000 diffractometer at 293 K. Crystals are monoclinic, a = 20.381(4), b = 9.462(2), 20.411(4) Å, β = 112.395(4)°, space group P21/c, Z = 4 M = 852.3, F(000) = 1696, µ[MoK& agr;] = 18.25 cm^-1. Intensities of 27979 reflections were measured and 10473 independent reflections were used for further refinement. The refinement was converged to wR2 = 0.0623 and GOF = 0.980 for all independent reflections [R1 = 0.0325 was calculated against F2 for 5790 observed reflections with I > 2 σ(I)]. Experimental and crystal data were submitted to Cambridge Crystallographic Data Centre.

For example: 2-(2-Pyridyl)ethynyldiphenylphosphane(3g): Yield: 93%; light yellow solid; mp 32 °C. ³¹P{H} NMR (162.6 MHz, CDCl₃): δ = -34.44 (s). ¹H NMR (400 MHz, CDCl₃): δ = 6.98 (m, 1 H), 7.19 (m, 1 H), 7.21 (m, 7 H), 7.37 (m, 1 H), 7.61 (dt, 4 H, J = 1.4 Hz), 8.43 (m, 1 H). ¹³C NMR (100.6 MHz, CDCl₃): δ = 86.11 (d, J = 9.8 Hz), 106.22, 122.74, 126.78, 128.15 (d, J = 7.6 Hz), 128.69, 132.30 (d, J = 21.3 Hz), 134.79 (d, J = 7.5 Hz), 135.55, 142.04, 149.46. (3-Methoxyprop-1-ynyl)(diphenyl)phosphane(3j): Yield: 49%; light yellow oil; bp 160 °C/0.1 Torr. ³¹P{H} NMR (162.6 MHz, CDCl₃): δ = -34.62 (s). ¹H NMR (400 MHz, CDCl₃): δ = 3.31 (s, 3 H), 4.17 (s, 2 H), 7.24 (m, 6 H), 7.61 (dt, 4 H, J = 1.7 Hz). ¹³C NMR (100.6 MHz, CDCl₃): δ = 57.23, 60.20, 83.22 (d, J = 7.6 Hz), 104.36, 128.26 (d, J = 7.6 Hz), 128.72, 132.14 (d, J = 21.3 Hz), 135.59.