Related Experiment Video
Updated: Aug 18, 2026

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
1,2-vinyl and 1,2-acetylenyl migration in Rh(II) carbene reaction: remarkable bystander effect
Weifeng Shi1, Fengping Xiao, Jianbo Wang
1Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.
Abstract:
A series of beta-(trichloroacetyl)amino alpha-diazo carbonyl compounds have been synthesized, and their Rh(II)-catalyzed reaction was investigated. 1,2-Migration was the predominant reaction pathway, and the migratory aptitude was found to be dramatically affected by the beta-substituents. The 1,2-vinyl and 1,2-acetylenyl group migration occurs preferentially in the presence of beta-hydrogen in Rh(2)(OAc)(4)-catalyzed reaction of beta-(trichloroacetyl)amino alpha-diazo carbonyl compounds. A possible reaction mechanism is discussed.
Related Concept Videos
Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation
The carbonyl center is activated by...
Electrophilic 1,2- and 1,4-Addition of HX to 1,3-Butadiene
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
Alkenes via Reductive Coupling of Aldehydes or Ketones: McMurry Reaction
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Diels–Alder Reaction Forming Bridged Bicyclic Products: Stereochemistry

