Chemoselective Schmidt Reaction Mediated by Triflic Acid: Selective Synthesis of Nitriles from Aldehydes

Abstract

An excellent utility of Schmidt reaction of aldehydes to access corresponding nitriles in an instantaneous reaction is demonstrated. The reaction of aldehydes with NaN(3) and TfOH furnishes the corresponding nitriles in near quantitative yields and tolerates a variety of electron-withdrawing and electron-donating substituents on the substrates. Formanilides, a common side product in Schmidt reaction, is not observed in this reaction. Besides these advantages, the salient feature of this reaction is that it exhibits a remarkable chemoselectivity, as acid and ketone functionalities are well tolerated under the reaction conditions. The reaction is easily scalable, high yielding, and nearly instantaneous.

Toluene Dioxygenase‐Catalysed Oxidation of Benzyl Azide to Benzonitrile: Mechanistic Insights for an Unprecedented Enzymatic Transformation

“…Another possibilityf or the transformation of 8 into 3 is that hydroxyazide 9 could be transformed to benzonitrile by a Schmidtr eaction [21] in the TDO active site, promoted by ap roton transfer.H owever, the evidence of nitrile formation from benzaldoximes as wella st he formation of 6 in the biotransformation of phenylethylazide makes this mechanism less probable and favourso ur proposed route. Ap ossible explanation for the formation of 6 is coordination of the startingm aterial with Fe II to promote N 2 loss and thus formation of the corresponding metal-nitrene complex (Scheme 5).…”

Direct Synthesis of Nitriles from Aldehydes and Hydroxylamine Hydrochloride Catalyzed by a HAP@AEPH2-SO3H Nanocatalyst

“…(BMIM ¼ 1-butyl-3-methyl-imidazolium), [19] acetohydroxamic acid/Bi(OTf) 3 , [20] CuO NPs, [21] CeCl 3 Á7H 2 O/KI/H 2 O 2 , [22] triflic acid, [23] and electrochemical methods. [24] However, earlier synthetic methods suffered from one or more of the following drawbacks: the use of strong acids or bases or oxidants, prolonged reaction time, low yield, requirement of excess reagents/catalysts, laborious work-up procedures, or harsh reaction conditions.…”

Natural product-inspired rational design, synthesis and biological evaluation of 2,3-dihydropyrano[2,3- f ]chromen-4(8 H )-one based hybrids as potential mitochondrial apoptosis inducers

“…The overall yield in achieving the synthesis of compound 11 from b-resorcylic acid (1) is 33.89%. Further, 2-amino-1,3,4-thiadiazoles 14a-f were prepared [47] by reaction of nitrile 12 [48] with thiosemicarbazide 13 in trifluroaceticacid (TFA) at 60e70 C (Scheme 3).…”