The high facioselectivity in the epoxidation of 4-deoxypentenosides (4-DPs) by dimethyldioxirane (DMDO) correlates with a stereoelectronic bias in the 4-DPs' ground-state conformations, as elucidated by polarized-pi frontier molecular orbital (PPFMO) analysis.

The oxidation of 2-iodo-N,N-dialkylanilines with an excess of dimethyldioxirane in acetone affords 2-iodyl-N,N-dialkylaniline oxides, structural features of which are in agreement with the new heterocyclic system of benziodoxazole.

Density functional theory (DFT) (Becke3LYP functional and the D95 basis set) was used to study the influence of substitution on the dimethyldioxirane epoxidation reaction of six- and seven-membered cyclic enol ethers. In agreement with our previously reported experimental results, the calculations predict that substitution on the cyclic enol ether influences the level of diastereoselectivity. A...

Herein we describe the development of a reactor for continuous flow generation and use dimethyldioxirane (DMDO) its application to low-level epoxidation unsaturated polymers.

The relative reactivity of a series of nucleophiles that includes ethylene, sulfides, sulfoxides, amines, and phosphines toward dioxirane, dimethyldioxirane, carbonyloxide and dimethylcarbonyloxide has been U U Ž . U examined at the MP4r6-31G rrMP2r6-31G , QCISD T r6-31G rrMP2r631G , and B3-LYPr6-31G levels of theory. The barriers for the oxidations with Ž . dimethyldioxirane are higher up to 2...

α,β-Unsaturated oximes underwent electrophilic epoxidation with in-situ-generated dimethyldioxirane to give the corresponding epoxides in good yields. This reaction is an example of “carbonyl umpolung” by transformation α,β-unsaturated ketones their oximes. Nucleophilic ring-opening reactions afforded α-substituted products. Shi asymmetric proceeded moderate enantioselectivity.

This work addresses a new approach developed in our laboratory, consisting in the application of isolated dimethyldioxirane (DDO, 1a) labelled with ¹⁸O for synthesis of epoxidized glyceryl linoleate (Gly-LLL, 2). We expect that this work could contribute in improving analytical methods for the determination of epoxidized soybean oil (ESBO) in complex food matrices by adopting an ¹⁸O-labelled-ep...