Mechanistic Studies of Formal Thioboration Reactions of Alkynes.

ABSTRACT: Several formal heteroborylative cyclization reactions have been recently reported, but little physical-organic and mechanistic data are known. We now investigate the catalyst-free formal thioboration reaction of alkynes to gain mechanistic insight into B-chlorocatecholborane (ClBcat) in its new role as an alkynophilic Lewis acid in electrophilic cyclization/dealkylation reactions. In kinetic studies, the reaction is second-order globally and first-order with respect to both the 2-alkynylthioanisole substrate and the ClBcat electrophile, with activation parameters of ΔG^‡ = 27.1 ± 0.1 kcal mol^-1 at 90 °C, ΔH^‡ = 13.8 ± 1.0 kcal mol^-1, and ΔS^‡ = -37 ± 3 cal mol^-1 K^-1, measured over the range 70-90 °C. Carbon kinetic i

SUBMITTER: Issaian A 

PROVIDER: S-EPMC5826600 | biostudies-literature | 2017 Aug

REPOSITORIES: biostudies-literature