The development of the homologous Julia–Kocienski reaction has led to the discovery of two new reaction modes of epoxides with sulfones. These pathways allow rapid and direct access to a range of γ-sultones and γ-sultines.

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The development of the homologous Julia-Kocienski reaction has led to the discovery of two new reaction modes of epoxides with sulfones.T hese pathwaysa llowr apid and direct access to arange of g-sultones and g-sultines.

Sultones and Sultines via a Julia-Kocienski Reaction of Epoxides. -A seriesof sultones (III) and (V) are prepared by Julia-Kocienski reaction of epoxides with sulfone (II) in the presence of lithium hexamethyldisilazide. The reaction of chiral epoxides (X) and (XII) proceeds with retention of the stereochemistry to afford corresponding chiral -sultones (XI) and (XIII), resp., whilst the reaction of disubstituted epoxides (VI) and (VIII) proceeds with a single inversion of stereochemistry. Styrene oxide does not react under these reaction conditions, however, the BF 3-mediated reaction of (R)-styrene oxide in the presence of potassium hexamethyldisilazide leads to ring-opening product (XV) with inverted stereochemistry. Treatment of -hydroxysulfone (XV) with DBU affords -sultine (XVI), which is photolyzed to cyclopropylbenzene. -(SMITH, G. M. T.; BURTON, P. M.; BRAY*, C. D.; Angew. Chem., Int. Ed. 54 (2015) 50, 15236-15240, http://dx.

Direct Conversion of Epoxides into Aziridines with N-Arylphosphoramidates. -The method represents a concise atom economic improvement of existing procedures for such transformations. In contrast the aziridation using electron-rich phosphoramidates, electron-deficient phosphoramidates such as (VIc) require the addition of a Lewis acid. Phosphoramidates deriving from electron-rich anilines such as (VIIa) may decompose upon isolation. -(MINICONE, F.; ROGERS, W. J.; GREEN, J. F. J.; KHAN, M.; SMITH, G. M. T.; BRAY*, C. D.; Tetrahedron Lett. 55 (2014) 43, 5890-5891, http://dx.