4208-49-5Relevant articles and documents
The Goldilocks Principle in Phase Labeling. Minimalist and Orthogonal Phase Tagging for Chromatography-Free Mitsunobu Reaction
Szigeti, Mariann,Dobi, Zoltán,Soós, Tibor
, p. 2869 - 2874 (2018/03/09)
An inexpensive and chromatography-free Mitsunobu methodology has been developed using low molecular weight and orthogonally phase-tagged reagents, a tert-butyl-tagged highly apolar phosphine, and a water-soluble DIAD analogue. The byproduct of the Mitsunobu reactions can be removed by sequential liquid-liquid extractions using traditional solvents such as hexanes, MeOH, water, and EtOAc. Owing to the orthogonal phase labeling, the spent reagents can be regenerated. This new variant of the Mitsunobu reaction promises to provide an alternative and complementary solution for the well-known separation problem of the Mitsunobu reaction without having to resort to expensive, large molecular weight reagents and chromatography.
Protic acid immobilized on solid support as an extremely efficient recyclable catalyst system for a direct and atom economical esterification of carboxylic acids with alcohols
Chakraborti, Asit K.,Singh, Bavneet,Chankeshwara, Sunay V.,Patel, Alpesh R.
supporting information; experimental part, p. 5967 - 5974 (2009/12/24)
(Chemical Equation Presented) A convenient and clean procedure of esterification is reported by direct condensation of equimolar amounts of carboxylic acids with alcohols catalyzed by an easy to prepare catalyst system of perchloric acid immobilized on silica gel (HClO4-SiO2). The direct condensation of aryl, heteroaryl, styryl, aryl alkyl, alkyl, cycloalkyl, and long-chain aliphatic carboxylic acids with primary/secondary alkyl/cycloalkyl, allyl, propargyl, and long-chain aliphatic alcohols has been achieved to afford the corresponding esters in excellent yields. Chiral alcohol and N-t-Boc protected chiral amino acid also resulted in ester formation with the representative carboxylic acid or alcohol without competitive N-t-Boc deprotection and detrimental effect on the optical purity of the product demonstrating the mildness and chemoselectivity of the procedure. The esters of long-chain (>C10) acids and alcohols are obtained in high yields. The catalyst is recovered and recycled without significant loss of activity. The industrial application of the esterification process is demonstrated by the synthesis of prodrugs of ibuprofen and a few commercial flavoring agents. Other protic acids such as H2SO4, HBr, TfOH, HBF4, and TFA that were adsorbed on silica gel were less effective compared to HClO4-SiO2 following the order HClO4-SiO 2 ? H2SO4-SiO2 > HBr-SiO 2 > TfOH-SiO2 ? HBF4-SiO2 ≈ TFA-SiO2. When HClO4 was immobilized on other solid supports the catalytic efficiency followed the order HClO4-SiO 2 > HClO4-K10 > HClO4-Al 2O3 (neutral) > HClO4-Al2O 3 (acidic) > HClO4-Al2O3 (basic).
