52763-07-2Relevant academic research and scientific papers
One-pot silyl ketene imine formation-nucleophilic addition reactions of acetonitrile with acetals and nitrones
Downey, C. Wade,Robertson, Grace Ann L.,Santa, Jhonmattew,Flicker, Kari R.,Stith, William M.
supporting information, (2020/01/03)
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) and a trialkylamine base promote the conversion of acetonitrile to its silyl ketene imine in situ when acetonitrile is employed as solvent. Residual TMSOTf acts as a Lewis acid catalyst to activate acetals
Mukaiyama addition of (trimethylsilyl)acetonitrile to dimethyl acetals mediated by trimethylsilyl trifluoromethanesulfonate
Downey, C. Wade,Lee, Alice Y.-K.,Goodin, John R.,Botelho, Courtney J.,Stith, William M.
supporting information, p. 3496 - 3499 (2017/10/05)
(Trimethylsilyl)acetonitrile reacts smoothly with dimethyl acetals in the presence of stoichiometric trimethylsilyl trifluoromethanesulfonate (TMSOTf) to yield β-methoxynitriles. The ideal substrates for this reaction are acetals derived from aromatic aldehydes. Elimination to the corresponding α,β-unsaturated nitriles is observed as the major product in the case of electron-rich acetals. A mechanistic hypothesis that includes isomerization of the silylnitrile to a nucleophilic N-silyl ketene imine is presented.
Substrate evaluation of rhodococcus erythropolis SET1, a nitrile hydrolysing bacterium, demonstrating dual activity strongly dependent on nitrile sub-structure
Coady, Tracey M.,Coffey, Lee V.,O'Reilly, Catherine,Lennon, Claire M.
supporting information, p. 1108 - 1116 (2015/02/19)
Assessment of Rhodococcus erythropolis SET1, a novel nitrile hydrolysing bacterial isolate, has been undertaken with 34 nitriles, 33 chiral and 1 prochiral. These substrates consist primarily of β-hydroxy nitriles with varying alkyl and aryl groups at the β position and containing in several compounds different substituents α to the nitrile. In the case of β-hydroxy nitriles without substitution at the α position, acids were the major products obtained, along with recovered nitrile after biotransformation, as a result of suspected nitrilase activity of the isolate. Unexpectedly, amides were found to be the major hydrolysis product when the β-hydroxy nitriles possessed a vinyl group at this position. To probe this behaviour further, additional related substrates were evaluated containing electron-withdrawing groups at the α position, and amide was also observed upon biotransformation in the presence of SET1. Therefore this novel isolate has also demonstrated NHase activity with nitriles that appears to be substrate-dependent.
Nitrile biotransformations for the synthesis of enantiomerically enriched β2-, and β3-hydroxy and -alkoxy acids and amides, a dramatic O-substituent effect of the substrates on enantioselectivity
Ma, Da-You,Wang, De-Xian,Pan, Jie,Huang, Zhi-Tang,Wang, Mei-Xiang
, p. 322 - 329 (2008/09/19)
Rhodococcus erythropolis AJ270, a nitrile hydratase/amidase-containing microbial whole cell catalyst, is able to catalyze the hydrolysis of a number of β-hydroxy and β-alkoxy nitriles under very mild conditions. Both the efficiency and enantioselectivity of the biocatalysis, however, were strongly dependent upon the structures of both nitrile and amide substrates. When biotransformations of racemic 3-hydroxy-3-phenylpropionitrile and 2-hydroxymethyl-3-phenylpropionitrile gave low enantioselectivity, their O-methylated isomers underwent highly efficient and enantioselective biocatalytic reactions to afford highly enantioenriched β2- and β3-hydroxy amide and acid derivatives in excellent yield. The study has provided an example of simple and very convenient substrate engineering method to increase the enantioselectivity of the biocatalytic reaction.
Synthesis of hindered functionalized ethers via high-pressure addition of alcohols to acrylic compounds
Jenner, Gérard
, p. 4807 - 4810 (2007/10/03)
The phosphine-catalyzed 1,4-addition of alcohols to activated alkenes is studied from a synthetic point of view. α- or β-Substituted acrylic compounds react sluggishly or not at all. In this case, high-pressure activation can remove steric inhibition leading to good yields of the corresponding ethers. Reactions involving crotonic compounds (hindered β reaction center) show higher pressure dependence than the corresponding additions of alcohols to methacrylic analogs (free β reaction center). This is in agreement with the concept that sterically demanding reactions show enhanced sensitivity to pressure. The result, obviously, is of high synthetic value as pressure may be capable of removing steric inhibition.
