Palladium-Catalyzed Direct α-Arylation of Methyl Sulfones with Aryl Bromides

Abstract

A direct and efficient approach for palladium-catalyzed arylation of aryl and alkyl methyl sulfones with aryl bromides has been developed. The catalytic system affords arylated sulfones in good to excellent yields (73-90%).

Rhodium-catalyzed direct ortho-alkenylation of phenyl sulfones with alkynes utilizing sulfonyl function as modifiable directing group

“…8 We applied their arylation method to our (orthoalkenylated phenyl) methyl sulfone 3a for further functionalization. Thus, 3a (0.2 mmol) was treated with bromobenzene (4a) (0.4 mmol) in the presence of Pd(OAc) 2 (0.02 mmol), 5 (0.04 mmol), and LiOBu t (0.6 mmol) as catalyst, ligand, and base, respectively, in toluene (1 mL) at 125 C for 12 h (Scheme 6).…”

“…Mp 118e119 C (yellow powder), 53 mg (64%), isolated by column chromatography using hexane/ethyl acetate (3:1, v/v); 1 H NMR (400 MHz, CDCl 3 ) d 2.53 (s, 3H), 6.71 (s,1H),7.17e7.25 (m,10H),7.46 (dd,J¼1.3,7.5 Hz,1H),7.52 (dt,J¼1.4,7.7 Hz,1H),7.64 (dt,J¼1.4,7.5 Hz,1H),8.13 (dd,J¼1.2,8.0 Hz, 1H); 13 C NMR (100 MHz, CDCl 3 ) d 21. 9, 120.9, 123.3, 127.9, 128.0, 128.3, 128.5, 128.8, 129.1, 129.4, 129.6, 131.1, 132.3, 134.1, 134.4, 144.1, 149 7, 128.5, 128.60, 128.63, 130.2, 130.4, 130.6, 132.1, 132.8, 133.3, 133.6, 133.9, 134.8, 137.1, 139.1, 139.6, 143.3 6,130.0 (q,J¼32.5 Hz),130.3,131.0,131.1,132.6,133.7,139.2,139.6,141.0,142.0,142.6;HRMS (APCI) (m, 4H), 7.08e7.…”

“…approach toward such an important class of compounds. Furthermore, the sulfonyl directing group was found to be readily modified after the ortho-alkenylation through palladium-catalyzed a-arylation 8,9 and subsequent diastereoselective cyclization to afford the corresponding 2-arylthiochromane 1,1-dioxide derivatives. These new findings are described herein.…”

When cross-coupling partners meet indolylphosphines

“…Suzuki-Miyaura coupling, Direct C-H arylation Kwong and Walsh [24,57,[59][60][61][62] Amidole-phos (L3)…”

“…Relevant direct arylation studies were further explored by Walsh and co-workers, where they disclosed the first direct monoarylation of methyl sulfones with aryl bromides using Pd(OAc) 2 /NPCy o-Toldole-phos (L2c) catalyst (Table 7, entries [16][17] [59]. Good product yields with high selectivity for the monoarylated products were obtained.…”