Metal-free synthesis of cyano acrylates via cyanuric chloride-mediated three-component reactions involving a cascade consists of Knoevenagel condensation/cyano hydration/esterification

Abstract

The synthesis of cyano acrylates has been achieved via an organocatalytic domino Knoevenagel reaction, hydration and esterification under metal-free conditions without using any additional solvent.

Mechanistic considerations and characterization of ammonia-based catalytic active intermediates of the green Knoevenagel reaction of various benzaldehydes

“…He isolated catalytic intermediates and as a result of this laid the fundamentals of "organocatalysis" (6,7). Unfortunately, the impact of his research has not yet been valued by everyone (8)(9)(10)(11). Organocatalysis is the catalysis of reactions with small organic molecules and generally seen as a more environmentally friendly form of catalysis opposed to for example (toxic) transition metal catalysts (12,13).…”

Hypervalent Iodine(III)-Catalyzed Epoxidation of β-Cyanostyrenes

“…White solid; yield: 1.69 g (7.79 mmol, 78%); mp 84-86 C (Lit. 27 29,31 White solid; yield: 1.84 g (8.62 mmol, 86%); mp 90-92 C (Lit. 31 Cyano-3-(3,4-dimethoxyphenyl) 770, 833, 946, 1006, 1024, 1091, 1126, 1159, 1186, 1219, 1255, 1334, 1370, 1421, 1463, 1505, 1578, 1604, 1748, 2217, 2938, 2972 cm -1 .…”

“…Calcd for C 12 H 10 ClNO 2 : C, 61.16; H, 4.28; N, 5.94. Found: C, 61.20; H, 4.29; N, 5.90.Ethyl (E)-3-(4-Chlorophenyl)-2-cyanoacrylate (1p)27,29,30 White crystalline solid; yield: 1.92 g (8.21 mmol, 82%); mp 49-51 C (Lit. 30 mp 50-52 C); R f = 0.4 (EtOAc-hexane 1:49).IR (KBr):797, 831, 1010, 1019, 1077, 1093, 1198, 1286, 1309, 1364, 1410, 1445, 1478, 1490, 1613, 1650, 1721, 1754, 2223, 2957, 2989, 3036 cm -1 .1 H NMR (400 MHz, CDCl 3 ):  = 1.32 (t, J = 7.2 Hz, 3 H, CH 3 ), 4.31 (q, J = 7.2 Hz, 2 H, CH 2 ), 7.39 (d, J = 8.8 Hz, 2 H, ArH), 7.85 (d, J = 8.4 Hz, 2 H, ArH), 8.11 (s, 1 H, CH).…”

Cyanuric chloride-catalyzed thioacetalization for organocatalytic synthesis of thioacetals

“…[18][19][20][21][22] Some particular reactions involving the condensation of aldehydes such as acetalization, 23 transacetalization 24 and the deprotection of thioacetals have been also realized with TCT catalysis. 25 However, to the best of our knowledge, no report on TCT-catalyzed thioacetalization has been described.…”