Chemodivergent Synthesis of Oxazolidin-2-ones via Cu-Catalyzed Carboxyl Transfer Annulation of Propiolic Acids with Amines

Abstract

Carboxylic acids are widely found in natural products and bioactive molecules and have served as raw material compounds in industry. We now report the first example of copper­(I)-catalyzed carboxyl transfer annulation of propiolic acids with amines, thereby chemodivergently constructing the oxazolidine-2-ones. In this reaction, two kinds of key propargyamine intermediates were formed through sequential CuI/NBS-catalyzed oxidative deamination/decarboxylative alkynylation or CuI-catalyzed decarboxylative hydroamination/alkynylation. The advantages of this decarboxylative coupling/carboxylative cyclization are showcased in the atom economy, chemical specificity, and functional group tolerance.

Selectivity Controlled Hydroamination of Alkynes to Sulfonyl Fluoride Hubs: Development and Application

“…For example, in 2017, Christopher and co-workers designed and synthesized a shelf-stable [4-(acetylamino)­phenyl]­imidodisulfuryl difluoride (AISF) (Scheme c), further demonstrating the utility of AISF as a −SO 2 F reagent . Complementary to these efforts and in our continuing interest in investigating functionalization toward the alkynyl moiety, we herein report a facile strategy to construct vinyl fluorosulfonimide frameworks via the hydroamination of alkynes with LiN­(SO 2 F) 2 (Scheme d). As LiN­(SO 2 F) 2 possesses both a nucleophilic nitrogen center and an electrophilic sulfur center, the challenge in controlling the chemoselectivity in the reaction is pretty obvious.…”

“…1 H NMR (400 MHz, chloroform-d) δ 7.48−7.41 (m, 1H), 7.30 (d, J = 7.9 Hz, 1H), 7.22 (dt, J = 9.6, 1.9 Hz, 1H), 7.17 (td, J = 9.8, 9.0, 3.2 Hz, 1H), 6.20 (d, J = 2.7 Hz, 1H), 5.92 (d, J = 2.6 Hz, 1H). 13 (d,J = 3.6 Hz,2H). 13 C{ 1 H} NMR (101 MHz, chloroform-d) δ 137.…”

“…The title compound was isolated by silica gel column chromatography (petroleum ether) as a light yellow oil in 76% yield (134.4 mg). 1 H NMR (400 MHz, chloroform-d) δ 7.25 (d,J = 7.5 Hz,2H),7.07 (d,J = 7.7 Hz,2H),5.90 (s,1H),5.58 (s,1H), 2.45 (t, J = 7.6 Hz, 2H), 1.45 (t, J = 7.4 Hz, 2H), 1.17 (s, 4H), 0.73 (t, J = 5.8 Hz, 3H). 13 C{ 1 H} NMR (101 MHz,141.6,130.2,129.4,125.8,119.4,35.8,31.6,30.9,22.6,14.1.…”

“…The title compound was isolated by silica gel column chromatography (petroleum ether) as a yellow oil in 55% yield (79.5 mg). 1 H NMR (400 MHz, chloroform-d) δ 7.50−7.39 (m, 10H), 6.65 (q, J = 7.1 Hz, 1H), 6.46 (q, J = 7.2 Hz, 1H), 2.09 (d,J = 7.1 Hz,3H),1.94 (d,J = 7.3 Hz,3H). 13 C{ 1 H} NMR (101 MHz, chloroform-d) δ 135.9, 134.9, 134.2, 134.1, 133.9, 132.2, 129.9, 129.6, 129.3, 129.1, 129.0, 125.5, 15.2, 14.5.…”

Synthesis of Furans via Rhodium(III)-Catalyzed Cyclization of Acrylic Acids with α-Diazocarbonyl Compounds

“…Carboxyl is an important functional group that are widely available in great structural diversity and at low cost . Considerable attention has been focused on the carboxyl directed aryl C–H functionalization, , and the property of decarboxylation of carboxylic acids in the reaction makes the carboxyl an attractive functionality that can be tracelessly removed after the C–H activation .…”