Iodosylbenzene-Trimethylsilyl azide

Magnus P, Lacour J, Weber W (1993) Direct A-alkyl azidonation of iV -dialkylatylamines with the iodosylbenzene/trimethylsilyl azide reagent combinatioiL J Am Chem Soc 115... 

Magnus P, Hulme C, Weber W (1994) alpha.-Azidonation of amides, carbamates, and ureas with the iodosylbenzene/trimethylsilyl azide reagent combination iV-acyUminium ion precursors. J Am Chem Soc 116(10) 4501-4502... 

Magnus P, Lacour J, Evans PA, Roe MB, Hulme C (1996) Hyptavalent iodine chemistry new oxidation reactions using the iodosylbenzene-trimethylsilyl azide reagent combination, direct a-and p-azido functionalization of triisojnxrpylsilyl enol ethers. J Am Chem Soc 118 (14) 3406-3418... 

Reaction of triisopropylsilyl enol ether with a combination of iodosylbenzene 18 and trimethylsilyl azide at -15 °C gives directly the /J-azido triisopropylsilyl enol ether 38 in a high yield. A mechanism involving the reductive -elimination of a-iodanyl onium ion 37, probably produced by ligand exchange of in situ generated PhI(N3)OTMS with silyl enol ether, was proposed. Addition of azide to the resulting a,/l-unsaturated onium ion explains the formation of 38 [58,59]. 

The treatment of iodosylbenzene (2) with two equivalents of trimethylsilyl azide in dichloromethane results in the formation of [azido(trimethylsilyloxy)iodo]-benzene (3) and [b/s(azido)iodo]benzene (4), (Scheme 2) [11 -14]. Although the azidoiodanes are unstable and decompose in solution at temperatures above -30°C, they can be employed in situ for azidonations of organic compounds. The addition of trimethylsilyl azide to iodosylbenzene/substrate mixtures enables such azidonations to be effected at temperatures higher than - 30 °C. 

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