94022-96-5Relevant articles and documents
Anti-Markovnikov alkene oxidation by metal-oxo–mediated enzyme catalysis
Hammer, Stephan C.,Kubik, Grzegorz,Watkins, Ella,Huang, Shan,Minges, Hannah,Arnold, Frances H.
, p. 215 - 218 (2017/10/19)
Catalytic anti-Markovnikov oxidation of alkene feedstocks could simplify synthetic routes to many important molecules and solve a long-standing challenge in chemistry. Here we report the engineering of a cytochrome P450 enzyme by directed evolution to catalyze metal-oxo–mediated anti-Markovnikov oxidation of styrenes with high efficiency. The enzyme uses dioxygen as the terminal oxidant and achieves selectivity for anti-Markovnikov oxidation over the kinetically favored alkene epoxidation by trapping high-energy intermediates and catalyzing an oxo transfer, including an enantioselective 1,2-hydride migration. The anti-Markovnikov oxygenase can be combined with other catalysts in synthetic metabolic pathways to access a variety of challenging anti-Markovnikov functionalization reactions.
Nucleophilic addition of arylmethylzinc reagents (ArCH2ZnCl) to formaldehyde: An easy access to 2-(hetro)arylethyl alcohols
Bhatt,Samant,Pednekar, Suhas
supporting information, p. 968 - 974 (2017/05/04)
The selective addition of arylmethylmagnesium halides with formaldehyde giving arylethyl alcohols is extremely challenging. To circumvent the difficulties, in the current communication, we have reported on the nucleophilic addition of benzyl zinc reagents derived from inexpensive and abundant benzyl chlorides to paraformaldehyde. The reaction investigated herein is hitherto unknown and was found to be selective, operationally simple, atom- and step-economical and high yielding to deliver phenethyl alcohols utilized as key perfumery ingredients in 60–83% yields. After successful establishment of the reaction condition, the reaction was also scaled up successfully to deliver a large-scale preparation of the phenethyl alcohol.
N-(phenylselenomethyl)phthalimide as new reagent for mild protection of alcohols as Pim-ethers
Temperini, Andrea,Minuti, Lucio
scheme or table, p. 2709 - 2711 (2012/07/16)
A mild activation of N-(phenylselenomethyl)phthalimide by iodonium ion in the presence of alcohols to give the corresponding O-phthalimidomethyl derivatives (Pim-ethers) is provided. Simple cleavage of the phthalimido group with ethylenediamine is also reported thus making this approach a new and efficient method of protecting alcohols.
