1501-94-6Relevant academic research and scientific papers
Aldehydes from Nitriles. Formation of N-Alkylnitrilium Ions and Their Reduction to N-Alkylaldimines by Organosilicon Hydrides
Fry, James L.,Ott, Roger A.
, p. 602 - 607 (1981)
A two-step procedure for the partial reduction of nitriles to aldehydes under mild reaction conditions is presented.This approach involves the N-alkylation of nitriles in dichloromethane solution and reductive capture of the resulting nitrilium ions to N-alkylaldimines with an organosilicon hydride such as triethylsilane or tri-n-hexylsilane.Mild hydrolysis of the aldimines produces aldehydes in generally good-to-excellent yield.Use of both triethyloxonium tetrafluoroborate and isopropyl chloride-iron(III) chloride reagents to effect alkylation is reported.Selective reduction of the nitrile function in polyfunctional substrates is possible with this technique.Over reduction to amines does not occur.Close control of reducing agent and reaction temperatures is not required.Attempts to effect reduction of nirile-boron trifluoride complexes with triethylsilane were unsuccessful, even at elevated temperatures.
Dissolving Metal Reduction of Esters to Alkanes. A Method for the Deoxygenation of Alcohols
Barrett, Anthony G. M.,Godfrey, Christopher R. A.,Hollinshead, David M.,Prokopiou, Panayiotis A.,Barton, Derek H. R.,et al.
, p. 1501 - 1509 (2007/10/02)
Divers carboxylic esters have been reduced with dissolving Group 1A metals.Using lithium in ethylamine, sterically hindered esters (RCO2R') were deoxygenated giving the alkane (R'H) whereas non-hindered esters regenerated the parent alcohol (R'OH).This permitted the selective deoxygenation of diesters.Conversely, potassium-sodium eutectic solubilised with 18-crown-6 in t-butylamine and tetrahydrofuran (THF) efficiently deoxygenated both hindered and non-hindered esters.In the absence of nucleophiles at ambient temperture the principal reaction of carboxylic ester radical anions was deoxygenation.
