N-(1-benzotriazol-1-ylalkyl)amides, versatile .alpha.-amidoalkylation reagents. 1. .alpha.-Amidoalkylation of CH acids

Abstract

finger (refluxing EtgO) affords pure [®Li]ethyllithiuin in 20-80% (typically 50-60%) isolated yields. For optimal results, the [®Li]ethyllithimn should be freshly sublimed before each use:

Comparative Studies on the Amidoalkylating Properties of N-(1-Methoxyalkyl)Amides and 1-(N-Acylamino)Alkyltriphenylphosphonium Salts in the Michaelis–Arbuzov-Like Reaction: A New One-Pot Transformation of N-(1-Methoxyalkyl)Amides into Phosphonic or Phosphinic Analogs of N-Acyl-α-Amino Acids

“…[4][5][6][7][8][9][10][11][12][13] The limitations and disadvantages of most of the above-mentioned amidoalkylating agents were reviewed by Katritzky et al 4,[14][15][16][17] Many of them (X = OR, Cl, Br) are relatively unstable compounds that cannot be stored for a prolonged period of time and thus have to be prepared in situ. Preparation of some of these amidoalkylating agents (X = Cl, Br) is relatively difficult or labor-consuming.…”

“…Most of them (X = OH, NHCOR, or 1-benzotriazolyl), including the most frequently used α-alkoxy derivatives (X = OR), require activation with Lewis acids, which are often quite expensive (e.g., ZrCl 4 , VCl 3 , CeCl 3 , or InCl 3 ). 4,[13][14][15][16][17] Application of Lewis acid has also been shown to diminish the activity of a reacting nucleophile and also necessitates a labor-consuming aqueous work-up procedure, which usually destroys the catalyst.…”

Benzotriazole-mediated amidoalkylations of nitroalkanes, nitriles, alkynes and esters

“…Previously malonates and acetoacetates 7 were reacted with 1 in the presence of anhydrous aluminum chloride and gave the amidoalkyated products of type 13 in moderate yields. The efficiency of the nucleophilic substitution of benzotriazole from compounds of type 1 is demonstrated by comparison of the electrophilic conditions.…”

“…Benzotriazole mediated amidoalkylations introduced in 1988, 6 offer advantages over previously reported methods as was already demonstrated for the amidoalkylation of (i) Grignards, 6 (ii) malonates and acetoacetates, 7 (iii) cyanide anion, 8 (iv) mercaptans and alcohols, 9 (v) electron-rich (hetero)aromatics, 10 and (vi) amines 11 (Scheme 1).…”

Synthesis of N‐Acyl‐N,O‐acetals from Aldehydes, Amides and Alcohols

“…Due to their importance several synthetic routes to Nacyl-N,O-acetals have been developed. Two of the most commonly employed syntheses are Katritzky's benzotriazole method [5] and the preparation via amido-sulfones. [6] In both methods, a suitable precursor, either an N-[α-(benzotriazol-l-yl)alkyl]amide or an α-amido-sulfone, is treated with sodium alkoxides.…”