52010-96-5Relevant articles and documents
Unique prototropy of meso-alkylidenyl carbaporphyrinoid possessing one meso-exocyclic double bond
Saha, Indrajit,Yoo, Jaeduk,Lee, Ji Hye,Hwang, Hyonseok,Lee, Chang-Hee
supporting information, p. 16506 - 16509 (2015/11/18)
Generic synthesis, identification of structural identity, unique prototropy and spectroscopic properties of meso-alkylidenyl-thia(m-benzi)porphyrinoid containing one exocyclic double bond at the meso-position were presented.
Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols
Hoover, Jessica M.,Stahl, Shannon S.
supporting information; experimental part, p. 16901 - 16910 (2011/12/04)
Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O2 as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)CuI/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups.
Reaction mechanisms and structural characterization of the reactive intermediates observed after the photolysis of 3-(hydroxymethyl)benzophenone in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions
Ma, Jiani,Li, Ming-De,Phillips, David Lee,Wan, Peter
, p. 3710 - 3719 (2011/06/22)
Nanosecond time-resolved resonance Raman (ns-TR3) spectroscopy was employed to investigate the photoinduced reactions of 3-(hydroxymethyl) benzophenone (1) in acetonitrile, 2-propanol, and neutral and acidic aqueous solutions. Density functional theory calculations were utilized to help the interpretation of the experimental spectra. In acetonitrile, the neutral triplet state 1 [denoted here as (m-BPOH)3] was observed on the nanosecond to microsecond time scale. In 2-propanol this triplet state appeared to abstract a hydrogen atom from the solvent molecules to produce the aryphenyl ketyl radical of 1 (denoted here as ArPK of 1), and then this species underwent a cross-coupling reaction with the dimethylketyl radical (also formed from the hydrogen abstraction reaction) to form a long-lived light absorbing transient species that was tentatively identified to be mainly 2-(4-(hydroxy(3- (hydroxymethyl)phenyl)methylene)cyclohexa-2,5-dienyl)propan-2-ol. In 1:1 H 2O:CH3CN aqueous solution at neutral pH, (m-BPOH) 3 reacted with water to produce the ArPK of 1 and then underwent further reaction to produce a long-lived light absorbing transient species. Three photochemical reactions appeared to take place after 266 nm photolysis of 1 in acidic aqueous solutions, a photoreduction reaction, an overall photohydration reaction, and a novel photoredox reaction. TR3 experiments in 1:1 H2O:CH3CN aqueous solution at pH 2 detected a new triplet biradical species, which is associated with an unusual photoredox reaction. This reaction is observed to be the predominant reaction at pH 2 and seems to face competition from the overall photohydration reaction at pH 0.
