A pseudopericyclic [3, 5]-sigmatropic rearrangement of a coumarin trichloroacetimidate derivative. Issue 6 (15th November 2017)

• Record Type: Journal Article
• Authors: Rajale, Trideep; Sharma, Shikha; Unruh, Daniel K.; Stroud, Daniel A.; Birney, David M.
• Is Part Of: Organic & biomolecular chemistry. Volume 16:Issue 6(2018)
• Page Start: 874
• Page End: 879
• Publication Date: 2017-11-15
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c7ob02335a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : A Woodward–Hoffmann forbidden, eight-centered transition state leads to the sole product of a pentadienyl imidate rearrangement. Abstract : Thermolysis of a coumarin trichloroacetimidate yields a single rearrangement product. The proposed mechanism is a pseudopericyclic allowed (Woodward–Hoffman forbidden) [3, 5]-sigmatropic rearrangement to form the corresponding amide followed by a sigmatropic [1, 5]-hydrogen migration. Transition state calculations at the B3LYP/6-31G(d, p) level support this mechanism and suggest the selectivity is influenced by the stability of the intermediates.