A Three‐Component Reaction to Construct β‐Aminonitroso‐α‐Diazocarbonyl Compounds under Metal‐Free Conditions

Abstract

A procedure for the transition-metal-free three-component reaction of 1,3,5-triazines, diazo compounds and tert-butyl nitrite has been described. This reaction goes through tandem nucleophilic attack to generate synthetically important β-aminonitroso-α-diazocarbonyl compounds in moderate to good yields. This protocol is distinguished by the use of readily available starting materials, wide substrate scope and operational simplicity. Notably, a NÀ N bond and a CÀ C bond were formed simultaneously.

TBAI-Catalyzed S–H and N–H Insertion Reactions of α-Diazoesters with Thiophenols and Amines under Metal-Free Conditions

“…1 Hz,2H),3.57 (s,2H), 2.31 (s, 3H), 1.22 (t, J = 7.1 Hz, 3H); 13 C{ 1 H} NMR (101 MHz,CDCl 3 ) δ 169.7,137.2,131.0,130.8,129.7,61.3,37.3,21.0,phenyl)thio)acetate (3c). Petroleum/ethyl acetate (20:1); colorless liquid (84.7 mg, 84% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (d,J = 8.4 Hz,2H),7.32 (d,J = 8.5 Hz,2H), 4.15 (q, J = 7.1 Hz, 2H), 3.60 (s, 2H), 1.30 (s, 9H), 1.21 (t, J = 7.1 Hz, 3H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 169. 8, 150.3, 131.2, 130.3, 126.0, 61.4, 37.0, 34.4, 31.1, 14.0.…”

“…Ethyl 2-((4-Methoxyphenyl)thio)acetate (3d). Petroleum/ethyl acetate (15:1); colorless liquid (70.5 mg, 78% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 7.42 (d,J = 8.3 Hz,2H),6.84 (d,J = 8.3 Hz,2H), 4.13 (q, J = 7.1 Hz, 2H), 3.79 (s, 3H), 3.51 (s, 2H), 1.21 (t, J = 7.1 Hz, 3H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 169. 8,159.5,134.1,124.8,114.5,61.2,55.2,38.5,thio)acetate (3e).…”

“…Petroleum/ethyl acetate (20:1); colorless liquid (81.3 mg, 95% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 7.44 (dd, J = 8.0, 5.4 Hz, 2H), 7.01 (t, J = 8.5 Hz, 2H), 4.15 (q, J = 7.1 Hz, 2H), 3.56 (s, 2H), 1.22 (t, J = 7.1 Hz, 3H); 13 3,133.4,133.0,131.3,129.1,61.6,36.7,phenyl)thio)acetate (3g). Petroleum/ethyl acetate (20:1); colorless liquid (103.5 mg, 98% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 7.54 (d,J = 8.2 Hz,2H),7.45 (d,J = 8.2 Hz,2H), 4.19 (q, J = 7.1 Hz, 2H), 3.71 (s, 2H), 1.24 (t, J = 7.2 Hz, 3H); 13 C{ 1 H} NMR (101 MHz, CDCl 3 ) δ 169.0, 140.5, 128.2 (q, J = 32.6 Hz), 128.0, 125.7 (q, J = 3.7 Hz), 124.0 (d,J = 273.2 Hz),61.8,35.2,14.0;19 F NMR (376 MHz,CDCl 3 ) δ -62.56.…”

“…7,157.8,131.5,128.6,122.3,120.9,110.5,61.2,55.6,34.9,thio)acetate (3j). Petroleum/ethyl acetate (20:1); colorless liquid (81.3 mg, 95% yield); 1 H NMR (400 MHz, CDCl 3 ) δ 7.46 (t, J = 7.5 Hz, 1H), 7.27 (dd, J = 13.7, 6.9 Hz, 1H), 7.13−7.03 (m, 2H), 4.13 (q, J = 7.1 Hz, 2H), 3.61 (s, 2H), 1.19 (t, J = 7.2 Hz, 3H); 13 (d,J = 22.2 Hz),61.4,35.8,35.7,13.9;19 F NMR (376 MHz, CDCl 3 ) δ -108.64.…”

“…Despite these significant achievements, these procedures typically require elaborately selected catalysts and the use of ligands or additives. Building on the work that iodine-catalyzed diazo activation toward olefin cyclopropanation and epoxidation could be well implemented by Li and our interest in the transformation reaction of diazo reagents, we envisioned that S–H and N–H insertion reactions of diazoalkanes in the presence of commercially available iodine anion catalysts could been implemented via a free carbene intermediate. Herein, we report S–H and N–H insertion reactions of thiophenols and amines with α-diazoesters using only commercially available TBAI as the catalyst under metal- and ligand-free conditions.…”