61066-88-4Relevant articles and documents
N-Heterocyclic Carbene/Carboxylic Acid Co-Catalysis Enables Oxidative Esterification of Demanding Aldehydes/Enals, at Low Catalyst Loading
Berkessel, Albrecht,Biswas, Animesh,Harnying, Wacharee,Sudkaow, Panyapon
supporting information, p. 19631 - 19636 (2021/08/09)
We report the discovery that simple carboxylic acids, such as benzoic acid, boost the activity of N-heterocyclic carbene (NHC) catalysts in the oxidative esterification of aldehydes. A simple and efficient protocol for the transformation of a wide range of sterically hindered α- and β-substituted aliphatic aldehydes/enals, catalyzed by a novel and readily accessible N-Mes-/N-2,4,6-trichlorophenyl 1,2,4-triazolium salt, and benzoic acid as co-catalyst, was developed. A whole series of α/β-substituted aliphatic aldehydes/enals hitherto not amenable to NHC-catalyzed esterification could be reacted at typical catalyst loadings of 0.02–1.0 mol %. For benzaldehyde, even 0.005 mol % of NHC catalyst proved sufficient: the lowest value ever achieved in NHC catalysis. Preliminary studies point to carboxylic acid-induced acceleration of acyl transfer from azolium enolate intermediates as the mechanistic basis of the observed effect.
Formation of α-SF5-enolate enables preparation of 3-SF5-quinolin-2-ones, 3-SF5-Quinolines, and 3-SF5-pyridin-2-ones: Evaluation of their physicochemical properties
Joliton, Adrien,Plancher, Jean-Marc,Carreira, Erick M.
supporting information, p. 2113 - 2117 (2016/02/18)
This study describes, for the first time, the generation of a SF5-substituted ester enolate from benzyl SF5-acetate under soft enolization conditions, which in turn participates in aldol addition reactions in high yield. The reaction was applied in the synthesis of 3-SF5-quinolin-2-ones, 3-SF5-quinolines, and 3-SF5-pyridin-2-ones, none of which have previously been reported. To provide guidelines for their use in drug discovery, the physicochemical properties of these building blocks were determined and compared with those of their CF3- and t-Bu-analogues.
'Me2CuLi·TMSCl in CH2Cl2'. The most powerful methylating agent for sterically congested α,β-enoates
Asao, Naoki,Lee, Sunyoung,Yamamoto, Yoshinori
, p. 4265 - 4266 (2007/10/03)
The reaction of Me2CuLi with sterically congested α,β-unsaturated esters in the presence of TMSCl in CH2Cl2 proceeded very smoothly to produce the conjugate addition products in high yields.