Platinum on Carbon‐Catalyzed Precise Reduction Control of Trichloromethyl to Geminal‐Dichloromethyl Groups

Abstract

Geminal-dichloromethyl derivatives could be efficiently synthesized by the highly chemoselective platinum on carbon-catalyzed mono-dechlorination of trichloromethyl substrates in dimethyl-

An Environmentally Benign, Catalyst‐Free N−C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides

“…2,2,2‐Trichloro‐ N ‐phenylacetamide [15e] (3E) : Using the experimental procedure EP‐1 , the product was obtained as white solid in 64 %; 1 H NMR (400 MHz, CDCl 3 ) δ 8.26 (s, 1H), 7.50 (d, J =8.3 Hz, 2H), 7.33 (t, J =7.7 Hz, 2H), 7.16 (t, J =7.6 Hz, 1H). 13 C NMR (100 MHz, CDCl 3 ) δ 136.05, 129.45, 126.18, 120.52.…”

“…N ‐Phenylbenzamide [15e] (3F) : Using the experimental procedure EP‐2 , the product was obtained as white solid in 83 %; 1 H NMR (400 MHz, DMSO‐d 6 ) δ 10.26 (s, 1H), 7.97 (d, J =7.2 Hz, 2H), 7.81 (d, J =8 Hz, 2H), 7.59 (t, J= 8.3 Hz, 1H), 7.53 (t, J =8.3 Hz, 2H), 7.36 (t, J =7.7 Hz, 2H), 7.10 (t, J =7.6 Hz, 1H). 13 C NMR (100 MHz, DMSO‐d 6 ) δ 165.57, 139.19, 135.01, 131.52, 128.85, 128.59, 128.36, 127.65, 123.64, 120.38.…”

Transition‐Metal‐Free Transformation of Aryl Bromides into Aromatic Esters and Amides via Aryl Trichloromethyl Ketones

“…2,2,2‐Trichloro‐4′‐(trifluoromethyl)acetophenone (3g): 14 Colorless oil (350 mg, 60 % yield). IR (neat): $\tilde {\nu}$ = 1719 cm –1 .…”

“…Benzyl 4‐Methylbenzoate (6bd): 15 White solid (371 mg, 82 % yield); m.p. 44–45 °C (ref 14. 45–46 °C).…”

Lewis Base‐Boryl Radicals Promoted Selective Mono‐ and Di‐ Hydrodechlorination of Trichloroacetamides and Acetates

“…As trichloromethyl substrates are easy to prepare and commercially available, [10] their selective removal of chlorine atom(s) offers a direct and conventional approach to yield the corresponding dichloromethyl or monochloromethyl counterparts for the respective uses in the field of medicines, synthetic chemistry, and materials science. Current dechlorination strategies involve the use of Pd/C [11] or Pt/C, [12] PPh 3 /MeOH, [13] PPh 3 /H 2 O, [14] HBr/H 2 O, [15] RMgX/NH 4 Cl, [16] and various transition metals [17] . Selective mono‐ and didechlorination of trichloromethyl group were disclosed by the Peters group where reduction with tributyltin hydride in THF at 60 °C delivered dichloro product while reaction in refluxing toluene afforded monochloro product instead [18] .…”