1524-12-5Relevant articles and documents
Efficient photolytic C-H bond functionalization of alkylbenzene with hypervalent iodine(iii) reagent
Sakamoto, Ryu,Inada, Tsubasa,Selvakumar, Sermadurai,Moteki, Shin A.,Maruoka, Keiji
supporting information, p. 3758 - 3761 (2016/03/25)
A practical approach to radical C-H bond functionalization by the photolysis of a hypervalent iodine(iii) reagent is presented. The photolysis of [bis(trifluoroacetoxy)iodo]benzene (PIFA) leads to the generation of trifluoroacetoxy radicals, which allows the smooth transformation of various alkylbenzenes to the corresponding benzyl ester compounds under mild reaction conditions.
Reaction pathway and rate-determining step of the Schmidt rearrangement/fragmentation: A kinetic study
Akimoto, Ryo,Tokugawa, Takehiro,Yamamoto, Yutaro,Yamataka, Hiroshi
experimental part, p. 4073 - 4078 (2012/06/29)
The Schmidt rearrangement of substituted 3-phenyl-2-butanone with trimethylsilyl azide in 90% (v/v) aqueous TFA gave two types of product, fragmentation and rearrangement, the ratio of which depends on the substituent: more fragmentation for a more electron-donating substituent. Rate measurements by azotometry indicated the presence of an induction period, and the pseudo-first-order rate constants showed saturation kinetics with respect to the azide concentration. It was indicated that the reaction proceeds through pre-equilibrium in the formation of iminodiazonium (ID) ion and that the N 2 liberation from the ID ion is rate-determining. Under high azide concentration conditions, where the effective reactant is the ID ion, the reaction gave a linear Hammett plot with a value of -0.50. The observed substituent effects on the rate and the product selectivity imply that path bifurcation on the way from the rate-determining TS to the product states occurs, as suggested by previous molecular dynamics simulations, in a similar manner to the analogous Beckmann rearrangement/fragmentation reactions.
Improved procedure for the reductive acetylation of acyclic esters and a new synthesis of ethers
Kopecky, David J.,Rychnovsky, Scott D.
, p. 191 - 198 (2007/10/03)
An optimized protocol for the DIBALH reductive acetylation of acyclic esters and diesters is described. This reductive acetylation procedure allows a wide variety of esters to be converted into the corresponding α-acetoxy ethers in good to excellent yields. It was found that, under mild acidic conditions, many α-acetoxy ethers can be further reduced to the corresponding ethers. This net two-step ester deoxygenation is an attractive alternative to the classical Williamson synthesis for certain ethers.