Halogen exchange reactions of perhalo-3-azaalkenes and their subsequent dehalogenation to form hetero-1,3-dienes

Cook, Michael I.; DesMarteau, Darryl D.

doi:10.1016/s0022-1139(00)81252-x

Cited by 5 publications

(3 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Section: Results and Discussionmentioning

confidence: 99%

“…Halide exchange was also attempted to give other halogen congeners, which would have been obtained if the rearrangement of other geminal azidohalides was successful. Unfortunately, the nucleophilic displacement by n-Bu 4 NCl was ineffective (eq 3), 47 and electrophilic activation with AlCl 3 afforded a complex mixture. 47 Although the cycloadditions of imidoyl fluoride are known, 48 5a was not a competent 2π partner for various reactive dienes such as cyclopentadiene, furan, and quadricyclane, even at high temperatures.…”

Section: Reaction Scope�alkyl and Benzoyl Migrationmentioning

confidence: 99%

“…Unfortunately, the nucleophilic displacement by n-Bu 4 NCl was ineffective (eq 3), 47 and electrophilic activation with AlCl 3 afforded a complex mixture. 47 Although the cycloadditions of imidoyl fluoride are known, 48 5a was not a competent 2π partner for various reactive dienes such as cyclopentadiene, furan, and quadricyclane, even at high temperatures. Danishefsky's diene underwent complex aldollike reactions, and oxaziridine formation with mCPBA was also unsuccessful.…”

Section: Reaction Scope�alkyl and Benzoyl Migrationmentioning

confidence: 99%

See 2 more Smart Citations

Fluorine-Assisted Rearrangement of Geminal Azidofluorides to Imidoyl Fluorides

2023

View full text Add to dashboard Cite

Organoazide rearrangement constitutes versatile synthetic strategies but typically requires an extremely strong acid and/or a high reaction temperature. Our group recently discovered the remarkable accelerating effect of the geminal fluorine substituent that enables the facile rearrangement of azides into imidoyl fluorides without the aid of acid under much milder reaction conditions. The role of geminal fluorine was elucidated by both experimental and computational investigations. This new reactivity led to the development of a practical one-step tandem preparative method for potentially useful and bench-stable imidoyl fluorides from a wide range of structurally diverse geminal chlorofluorides. Our additional efforts to expand the reaction scope regarding the migrating group, halogen, and carbonyl function are described, and the synthetic utility of the imidoyl fluoride products was demonstrated in hopes of promoting the use of this under-appreciated functional group in the synthetic organic community.

show abstract

Section: Results and Discussionmentioning

confidence: 99%

Section: Reaction Scope�alkyl and Benzoyl Migrationmentioning

confidence: 99%