Sulfoximinocarbonylation of aryl halides using heterogeneous Pd/C catalyst

Abstract

A heterogeneous Pd/C catalyzed three component protocol is developed for the sulfoximinocarbonylation of aryl halides.

Palladium(II)‐Catalyzed N‐Carbonylative Cross‐Coupling Reaction of Sulfoximines with Aryl, Heteroaryl, and Alkenyl Halides Using Tungsten Hexacarbonyl as Carbon Monoxide Source

“…N ‐(3‐Thiophene)‐S‐methyl‐S‐phenylsulfoximine (3p) : [21a] Method A : 40 mg (74%); R f =0.2 (EtOAc:Hexane=1 : 2); White solid; Melting Point: 117–119 °C; 1 H NMR (400 MHz, CDCl 3 ) δ 8.13 (td, J =9.6, 2.4 Hz, 2H), 8.07–8.05 (m, 2H), 7.80 (dd, J =3.7, 1.2 Hz, 1H), 7.71–7.67 (m, 1H), 7.64–7.60 (m, 2H), 7.48 (dd, J =4.9, 1.2 Hz, 2H), 3.46 (s, 3H); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ 169.0, 141.3, 139.0, 134.0, 132.2, 131.7, 129.8, 127.8, 127.3, 44.6; IR (KBr) 3076, 3040, 2928, 1688, 1490, 1409, 1247, 1345, 1218, 947 cm −1 .…”

“…[20] Additionally, Pd-catalyzed carbonylative coupling from sulfoximines with aryl halides in the presence of carbon monoxide has been demonstrated. [21] Metal carbonyl compounds, including Co 2 (CO) 8 , W(CO) 6 , and Mo(CO) 6 , have been applied as solid surrogates of carbon monoxide in organic synthesis [22] due to its high toxicity and difficulty in handling gaseous carbon monoxide. Recently, we developed Cu-TBAH-catalyzed N-arylation, Rh-catalyzed N-imi-dazolylation, N-imidoylation and N-oxoimidoylation and synthetic methods for Rh-catalyzed 1,2-benzothiazines and indolo-1,2-benzothiazines.…”

Supported Palladium Catalyzed Carbonylative Coupling Reactions using Carbon Monoxide as C1 Source

“…Recently, Sekar and group developed a strategy for Pd/C catalyzed sulfoximinocarbonyaltion of aryl halides (X=I, Br) (Scheme 35). [56] They obtained considerably excellent yields of the sulfoximinocarbonylated products with recyclability of the catalyst up to five cycles without any loss in catalytic activity.…”

N−H and C−H Functionalization of Sulfoximine: Recent Advancement and Prospects

“…In 2016, first example of palladium catalyzed carbonylation of NH ‐sulfoximines with aryl halides (X=I, Br) under simple reaction condition to synthesize a broad array of N ‐aroylated derivatives 27 in good to excellent yields came from the laboratory of Prof. Sekar and co‐workers (Scheme 41). [55] A brew of 1 mol % Pd/C as heterogeneous catalysts, 1 equiv. of K 2 CO 3 as base and carbon monoxide gas as CO surrogate in DMF at 80 °C was identified as utmost to achieve to fine conversion albeit a higher catalyst loading and reaction temperature was necessary for aryl bromides.…”