Cesium Carboxylate-Promoted Iridium Catalyzed C–H Amidation/Cyclization with 2,2,2-Trichloroethoxycarbonyl Azide

Abstract

An Ir(III)-catalyzed direct C-H amidation/cyclization of benzamides using 2,2,2-trichloroethoxycarbonyl azide (TrocN3) as the aminocarbonyl source is reported. With the aid of cesium carboxylate, the reactions proceed efficiently and with high regioselectivity, producing various functionalized quinazoline-2,4(1H,3H)-diones, which are important building blocks and key synthetic intermediates for biologically and medicinally important compounds. During the reactions, two new C-N bonds were formed by breaking C-H and N-H bonds sequence.

Synthesis of 7‐Azaindole Amidated Derivatives: An Efficient Usage of Acyl Azides as the Nitrogen Source

“…Recently, Chang and co‐workers reported developed a pioneering work on the Ir(III) and Ru(II) catalyzed C−H amidation reactions of arenes and alkenes with various acyl azides to form C−N bond by altering catalyst system ,. From then on, a wide variety of direct C−N amidation reactions using acyl azides as amidating reagents have been reported –. However, to the best of our knowledge, there is only one example of controlling the orthogonal reactivity of acyl azides between C−C and C−N amidations by the choice of catalyst system, and the dual activity of acyl azides has not been well explored …”

ZnO nanoparticles supported on dendritic fibrous nanosilica as efficient catalysts for the one-pot synthesis of quinazoline-2,4(1H,3H)-diones

“…White solid, mp: 189–191 °C (lit. : 168–169 °C), 52 IR (KBr, ν , cm −1 ): 3462, 3067, 2975, 2921, 2849, 1717, 1672,1589, 1435, 1190, 1122, 754, 717, 692, 536. 1 H NMR (CDCl 3 , 400 MHz) δ = 10.01 (br s, 1H), 7.98 (dd, J = 7.9, 0.7 Hz, 1H), 7.60–7.54 (m, 1H), 7.14–7.10 (ddt, J = 7.7, 7.1, 0.7 Hz, 1H), 6.98–6.95 (m, 1H), 1.78 (s, 9H) ppm.…”

“…White solid, mp: 168–170 °C (lit. : 173–174 °C), 52 IR (KBr, ν , cm −1 ): 3467, 3353, 3197, 2928, 1714, 1642, 1535, 1430, 1288, 1163, 814, 786, 651, 548. 1 H NMR (CDCl 3 , 400 MHz) δ = 9.78 (br s, 1H), 7.90 (d, J = 8.1 Hz, 1H), 6.99 (ddd, J = 8.1, 1.5, 0.6 Hz, 1H), 6.82–6.79 (m, 1H), 2.38 (s, 3H), 1.82 (s, 9H) ppm.…”

“…White solid, mp: 182–184 °C (lit. : 189–190 °C), 52 (KBr, ν , cm −1 ): 3417, 3344, 3206, 2932, 1716, 1640, 1532, 1440, 1288, 1156, 814, 735, 642, 527. 1 H NMR (CDCl 3 , 400 MHz) δ = 10.08 (br s, 1H), 7.79 (s, 1H), 7.40–7.32 (m, 1H), 6.93 (d, J = 8.2 Hz, 1H), 2.34 (s, 3H), 1.75 (s, 9H) ppm.…”

Organic Azides: Versatile Synthons in Transition Metal‐Catalyzed C(sp2)−H Amination/Annulation for N‐Heterocycle Synthesis

“…achieved the practical synthesis of quinazoline‐2,4(1 H ,3 H )‐diones from benzamides and 2,2,2‐trichloroethoxycarbonyl azide (TrocN 3 ) via Ir(III)‐catalyzed C−H amidation/cyclization (Scheme 23). [31] The combination of [IrCp*Cl 2 ] 2 and AgNTf 2 was demonstrated as the efficient catalytic system and no desired product was detected with the use of other metal catalysts such as Pd(OAc) 2 , [RhCp*Cl 2 ] 2 and Co(acac) 2 . 2,2,2‐Trichloroethoxycarbonyl azide (TrocN 3 ) acted as a good aminocarbonyl source in this reaction, while other azides bearing different leaving groups led to inferior results.…”