Metal‐and Base‐Free Oxidative Cleavage of C(O)−C Bond in Ketones to Access Esters

Abstract

A novel strategy to selective cleavage and esterification of C(CO)−C bonds is described. The efficient approach showed a prominent merit compared to previously reported systems, without high temperature, high pressure, inert gas protection, and transition‐metal free. Meanwhile, a rational C−C bond cleavage possible mechanism is proposed by the control experiments.

Efficient Synthesis of Esters by Cleavage of C–S and C–N Bonds via Alkylation and Activation of Thioamides

“…Methyl Biphenyl-4-carboxylate (3aa) 15,16 White solid; yield: 0.186 g (88%); mp 114.0-116.0 °C. IR (neat): 1708, 1267, 1111, 752 cm -1 .…”

“…1 H NMR (500 MHz, CDCl 3 ):  = 8.09 (dt, J = 8.5, 2.0 Hz, 2 H), 7.63 (dt, J = 8.5, 3.7 Hz, 2 H), 7.58-7.61 (m, 2 H), 7.42-7.46 (m, 2 H), 7.37 (tt, J = 7.4, 2.6 Hz, 1 H), 3.91 (s, 3 H). 13 Methyl 2-Naphthoate (3ba) [15][16][17] White solid; yield: 0.167 g (90%); mp 78-80 °C. IR (neat): 1705, 1292, 1205, 1129, 785, 767 cm -1 .…”

“…IR (neat): 1720, 1282, 1225, 1042, 754 cm -1 . Methyl 3,4-Dimethoxybenzoate (3fa) 15,18 White solid; yield: 0.109 g (56%); mp 58-60 °C.…”

“…13 C NMR (125 MHz, CDCl 3 ):  = 166.4, 153.3, 152.9, 120. Methyl 4-Methylbenzoate (3ia) 15,17 Colorless oil; yield: 0.105 g (70%).…”