Reactions of norcarane and of norborn-2-ene with iodine(I) azide and iodine(I) chloride

Cambie, R. C.; Dixon, Graham; Rutledge, P. S.; Woodgate, Paul D.

doi:10.1039/p19820000961

Cited by 8 publications

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“…Iodine azide was first synthesized from AgN 3 and I 2 , and methods associated with its preparation and reactivity are the most abundant in the literature. Hassner and co-workers − made significant contributions to the understanding of the mechanism of halogen azide addition to alkenes, and his original procedures for the formation of IN 3 (from ICl + NaN 3 − or I 2 + NaN 3 − ) became popular among those disposed to use the reagent for synthetic purposes. Several alternatives soon followed, including those with thallium (TlN 3 ) or stannous (Bu 3 SnN 3 ) reagents as the source of azide ion, − but these and other methods did not find widespread application.…”

Section: Introductionmentioning

confidence: 99%

Taming Chlorine Azide: Access to 1,2-Azidochlorides from Alkenes

2015

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The in situ preparation and trapping of chlorine azide provided a versatile one-pot method for the azidochlorination of alkenes. Gaseous ClN3 generated from sodium azide, hypochlorite, and acetic acid can be explosive if isolation is attempted. Instead, we generated the reagent in biphasic media in the presence of olefinic compounds dissolved in the organic layer or evenly emulsified throughout the solution in the absence of organic solvent. Under these conditions, ClN3 is created slowly and trapped immediately at the aqueous-organic interface. The resulting safe and reliable procedure provided 1,2-azidochloride derivatives of a variety of substrates, with evidence for both polar and radical mechanisms. Minor impurities characterized in the product mixtures indicated the presence of alternative reaction pathways deriving primarily from radical intermediates.

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