769-61-9Relevant articles and documents
Salt Effects on the Intramolecular Cannizzaro Reaction of Phenylglyoxal. Specific Acceleration by Calcium Ion
Okuyama, Tadashi,Kimura, Kazumasa,Fueno, Takayuki
, p. 2285 - 2286 (1982)
Effects of added salts on the rate of alkaline rearrangement of phenylglyoxal to mandelic acid were examined in aqueous solution at 30 deg C.The reaction showed positive salt effects.Specific acceleration was found with some metal ions, the efficiency decreasing in the order Ca2+>Tl+>Sr2+>Ba2+.
Selective Transformation of Vicinal Glycols to α-Hydroxy Acetates in Water via a Dehydrogenation and Oxidization Relay Process by a Self-Supported Single-Site Iridium Catalyst
Shen, Lingyun,Chen, Zhe-Ning,Zheng, Qingshu,Wu, Jiajie,Xu, Xin,Tu, Tao
, p. 12833 - 12839 (2021/10/29)
α-Hydroxy acids have attracted broad attention because of their prevalence in bioactive molecules and biodegradable polymers, but their conventional syntheses are usually restricted to aromatic substrates, especially, in a stepwise manner. Herein, we disclose the transformation of alkyl and aryl vicinal glycols to α-hydroxy acetates in water under the air atmosphere with our solid self-supported NHC-Ir single-site catalyst. Both aliphatic and aromatic glycols are compatible with a much higher catalytic efficiency in the presence of this solid single-site catalyst than other viable molecular catalysts (93% vs a dehydrogenation facilitated by the catalyst, and then it proceeds through an unexpected oxidization relay step by oxygen in the air, leading to the α-hydroxy acetate formation. Our protocol can potentially contribute to the valorization of readily available and inexpensive diols.
Primary Kinetic Isotope Effects in Hydride Transfer: Experimental Studies of Intramolecular Hydride Migration and ab initio Molecular Orbital Calculations of Model Systems.
Hillier, Ian H.,Smith, Stephen,Mason, Stephen C.,Whittleton, Stephen N.,Watt, C. Ian F.,Willis, Julie
, p. 1345 - 1352 (2007/10/02)
Measurements of the primary kinetic hydrogen isotope effects for the intramolecular migration of hydride accompanying the rearrangements of (i) hydroxy-ketones involving 1,4-migration of hydride between ketonic carbonyl groups and (ii) phenylglyoxal hydrates to their corresponding mandelic acids are described.The results are discussed using ab initio MO calculations od model systems, with a variety of basis sets.The value of such model calculations is demonstrated.