10.1021/jo00231a046
The research focuses on the development of a more efficient and convenient method for allylic and benzylic oxidations using a reagent system comprised of tert-butyl hydroperoxide and pyridinium dichromate. The purpose of this study was to address the drawbacks of traditional chromium(VI)-based oxidation methods, such as the use of large excess reagents, large volumes of solvents, and long reaction times. The researchers found that the combination of these two reagents in a 1:1 molar ratio effectively facilitated the oxidation process under mild conditions, yielding high conversion rates and product yields. The chemicals used in the process included tert-butyl hydroperoxide, pyridinium dichromate, and various substrates such as cholesteryl acetate, dicyclopentadiene, citronellol acetate, 1-phenylcyclohexene, α-pinene, A3-carene, cycloheptene, limonene, fluorene, diphenylmethane, and tetralin, among others. The conclusions of the research highlighted the utility and simplicity of the tert-butyl hydroperoxide-pyridinium dichromate method, suggesting its potential for wide application in organic synthesis.
10.1021/jo00109a043
The research focused on studying the kinetic parameters and relative energies of radicals involved in the rearrangement of a bicyclic cyclopropylmethylhomoallyl system. The purpose was to understand the effects of benzylic stabilization on the cyclopropylmethyl radical, which facilitates the characterization of all four ring-opening and closing processes. The study concluded that benzylic stabilization does not significantly perturb the position of the transition state for ring opening, suggesting that phenyl substitution of a bicyclic cyclopropylmethyl radical can be a useful tool for analyzing the effects of substituents elsewhere in the system. Key chemicals used in the process included bicyclo[3.1.0]hexan-1-yl, Bu3SnH, PhSH, and t-BuSH as radical traps, as well as a series of synthesized compounds such as 1-phenylbicyclo[3.1.0]hexane, 3-methyl-1-phenylcyclopent-1-ene, and 1-phenylcyclohexene. The research provided insights into the regioselectivity of ring opening and the energetics of isomeric homoallyl radicals, which are valuable for the rational application of cyclopropylmethyl radical rearrangements in organic synthesis.
10.1021/ol020229e
The research discusses the investigation of ketones containing N-aryl-substituted oxazolidinones for the asymmetric epoxidation of olefins, specifically cis-β-methylstyrene, styrene, and 1-phenylcyclohexene. The purpose of the study was to understand the electronic effects on the enantioselectivity of the epoxidation process and to identify factors that influence the interaction between the phenyl group of the olefin and the oxazolidinone of the catalyst. The researchers found that the introduction of electron-withdrawing groups onto the N-phenyl group of the catalyst enhanced the attractive interaction, leading to higher enantioselectivity.