Rhodium Acetate-Mediated Epoxidation from the Reaction of Diazobenzyl­phosphonates with Aldehydes and a Ketone: A Convenient and Highly Stereoselective Synthetic Method of cis-1,2-Epoxypropylphosphonates

Abstract

The first stereoselective synthetic route to 1,2-epoxyalkylphosphonates from the reaction of dimethyl diazophosphonate with aldehydes or a ketone using a dirhodium complex as catalyst is reported. The experimental results showed that only a single isomer of the epoxide product was obtained from the catalytic reaction, which gave (1R ^* ,2S ^* )-(Z)-1,2-epoxyalkylphosphonate in good yield and completely chemoselectively without the formation of the 1,3-dipolar cycloaddition product 1,3-dioxolane.

Key words

1,2-epoxyalkylphosphonates - rhodium acetate - epoxidation - stereoselectivity

References

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18

Selected bond lengths [Å] and bond angles [°]: P-O6: 1.457 (6), P-O4: 1.565 (6), P-O5: 1.5681 (15), P-C7: 1.820 (2), O1-C8: 1.430 (3), O1-C7: 1.448 (2), C7-C8: 1.485 (3), C6-C7: 1.500(3), C8-C9: 1.495 (3), C8-H8: 0.980; C8-O1-C7: 62.10 (13), O1-C7-C8: 58.38 (13), O1-C8-C7: 59.52 (13), O1-C7-P: 114.34 (14), O1-C8-H8: 114.30.

19

Typical procedure for the epoxidation of arylaldehydes or ketones with dimethyl diazophosphonate. A solution of aldehyde or ketone (2.4 mmol), catalyst (0.09 mmol), and diazophosphonate (2.2 mmol) in toluene (10 mL) was heated to reflux under an argon atmosphere. The reaction was monitored by TLC. After the reaction was complete, the mixture was cooled to room temperature and the solvent was removed in vacuo, and a portion of the crude product was subjected to ¹H NMR analysis to determine the isomer ratio. The crude product was purified by column chromatography on silica gel using petroleum ether-EtOAc, 3:1 as eluent to give epoxides.
Detailed spectral data of product 3, and the crystal data for compound 3f, are available upon request from the author.