Manganese(III)‐Promoted Double Carbonylation of Anilines Toward α‐Ketoamides Synthesis

Abstract

Employing anilines as nucleophiles in double carbonylation is a longstanding challenge. In this communication, a Mn(III)‐promoted double carbonylation of alkylborates or Hantzsch esters with anilines toward the synthesis of α‐ketoamides has been developed. By using easily available potassium alkyltrifluoroborates or Hantzsch esters as the starting material, and cheap and non‐toxic Mn(OAc)3 ⋅ 2H2O as the promotor, a broad range of alkyl α‐ketoamide derivatives were synthesized in moderate to good yields with excellent selectivity.

Photoredox‐ and Nickel‐Catalyzed Hydroalkylation of Alkynes with 4‐Alkyl‐1,4‐dihydropyridines: Ligand‐Controlled Regioselectivity

“…All reactions were carried out under dry nitrogen atmosphere by using standard Schlenk techniques unless otherwise stated. Starting materials including 2 a , [63] 2 b , [63] 2 c , [31] 2 d , [63] 2 e , [35] 2 f , [63] 2 g , [31] 2 h , [31] 2 i , [36] 2 j , [40] 2 k , [35,64] 2 l , [64] 2 m , [65] 2 n , [66] 2 o , [63] 2 p , [40] 2 q , [63] 2 r , [41] and 2 s [67] were prepared according to the literature procedures. Other reagents such as terminal and internal alkynes ( 1 a – 1 q and 5 ), fac ‐[Ir(ppy) 3 ], [Ir{dF(CF 3 )ppy} 2 (dtbbpy)]BF 4 , fac ‐[Ir(Fppy) 3 ], anhydrous NiCl 2 , [NiCl 2 (PPh 3 ) 2 ], [NiCl 2 (dppe)], [NiCl 2 (dtbbpy)], [Ni(acac) 2 ], NiBr 2 ⋅ diglyme, [NiCl 2 (dme)], NiCl 2 ⋅ 6 H 2 O, TEMPO, starting materials for the preparation of 2 a – 2 s and 10 a , reagents for measurements, and solvents were purchased from commercial sources.…”

Photoredox-catalyzed carbonylative acylation of styrenes with Hantzsch esters

“…Our group reported a Mn-mediated double carbonylative reaction to synthesize dicarbonyl compounds by employing Hantzsch esters as a precursor, but excess loading of catalyst was required in this reaction. 12 Herein, we developed a three-component reaction of the radical precursors produced by Hantzsch esters, CO and styrenes under a blue light environment in the presence of a photo-catalyst without any other additives (Scheme 1c).…”