Study On the Electrophilic Tellurolactonization of 1,2-Allenic Phosphonates: A Facile and Efficient Synthesis of 4-(Phenyltelluro)-1,2-oxaphosphol-3-ene 2-Oxides

Abstract

The electrophilic cyclization of 1,2-allenic phosphonates with in-situ-generated PhTeX to afford 4-(phenyltelluro)-2-methoxy-2,5-dihydro[1,2]-oxaphosphole 2-oxides was studied. Good yields were observed when PhTeBr was used as the electrophilic reagent. The stereochemistry of the reaction is also discussed in the paper.

Key words

1,2-allenic phosphonates - tellurolactonization - electrophilic - phosphorus heterocycles

References and Notes

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Typical Experimental Procedure: To a solution of diphenyl ditelluride (0.6 mmol) in anhyd MeOH (2 mL) was added dropwise a solution of Br₂ (0.60 mmol) and MeOH (1.2 mL) under nitrogen atmosphere. The mixture was stirred at r.t. for 2 h. Then 1,2-allenic phosphonates 1 (1.0 mmol) in anhyd MeOH (2 mL) was added to the above PhTeBr solution with stirring, and the reaction mixture was heated to 55°C. After the reaction was complete (2 h), the mixture was concentrated and the residue was purified by flash chromatography to afford 4-(phenyltelluro)-1,2-oxaphosphol-3-ene 2-oxides 2. Compound 2a: white solid; mp 148-150 °C. ¹H NMR (400 MHz, CDCl₃): δ = 7.85-7.87 (m, 2 H), 7.29-7.49 (m, 3 H), 5.59 (d, J = 30.3 Hz, 1 H), 3.69 (d, J = 11.9 Hz, 3 H), 1.61 (s, 3 H), 1.55 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 156.5 (d, J = 15.1 Hz), 140.9, 130.2, 129.9, 117.3 (d, J = 154.0 Hz), 111.0, 89.2 (d, J = 11.0 Hz), 53.3 (d, J = 6.5 Hz), 29.6 (d, J = 2.4 Hz), 28.8 (d, J = 1.5 Hz). IR (KBr): 2978, 2674, 1651, 1545, 1458 cm^-1. MS (EI): m/z (%) = 368(40) [M⁺], 77(100), 102(76), 51(74), 43(53), 67(46).

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CCDC 661519 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [e-mail], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: [phone].