Photochemical and thermal rearrangement of oxaziridines. Experimental evidence in support of the stereoelectronic control theory

Abstract

The irradiation of an optically pure isomer of a spirooxaziridine, (2f?,o'5')-6(e)-reri-butyl-2-(a:-methylbenzyl)l,2-oxazaspiro[2.5.]octane, gave a single lactam, (5S,aS)-5-/ert-butyl-l-(a:-methylbenzyl)hexahydro-2-azepinone. The absolute configurations of these two compounds were established by chemical methods and X-ray crystal structure analysis. The comparison between the configurations of the reactant and product leads to the conclusion that the C-C bond cleaved is the bond in the anti position with respect to the lone pair of the oxaziridine nitrogen atom. This work provides clear evidence in support of

Retracted: Development of the generation of alkyl radicals from N‐tosyloxaziridines

“…[2] The amination also occurs with enolates, [3] alkoxides, [4] sulfides [5] and even organometallic species [6] with moderate to excellent yields. Besides, oxaziridines undergo photochemical conditions leading to various rearrangements, [7] isomerizations [8] and eliminations. [9] Most of all, the predominant application of oxaziridines is as electrophilic oxygen donors.…”

Oxaziridine (C-CH3NO), C-CH2NO Radicals and Cl, NH2 and Methyl Derivatives of Oxaziridine; Structures and Quantum Chemical Parameters

“…In a work on photochemical and thermal rearrangement of oxaziridines bond lengths of N-O, C-O and C-N is 1.535Å, 1.428 Å and 1.456 Å respectively [24]. Furthermore in theoretical study of the mechanisms of iron-catalyzed amino hydroxylation reactions, 1.48 Å, 1.41 Å and 1.46 Å have been reported for N-O, C-O and C-N bond length respectively in N-sulfonyloxaziridine [12].…”

Synthesis and Utilization of Compounds with Chiral Nitrogen Centers

“…Spirooxaziridine 56 2537 Ä 8 h 56 57 R = (-)-(5)-a-phenylamine ([«ID -32.7°) was prepared by oxidation of the corresponding chiral inline, and its absolute configuration was determined by X-ray analysis (52). ]octane (56) at 2537 A gives the single lactam 57, having the S configuration at the ring tert-butyl carbon.…”