Catalytic synthesis of silyl formates with 1 atm of CO2 and their utilization for synthesis of formyl compounds and formic acid

Mechanistic studies on the N-formylation of amines with CO2 and hydrosilane catalyzed by a Cu–diphosphine complex

“…2 Additionally, silyl formate was reported to react with various amines, affording the corresponding formamides. 4,8 This encouraged us to clarify the formation of silyl formate as the reaction intermediate for the N-formylation of amines catalyzed by our Cu salt/diphosphine ligand catalyst system. To elucidate the reaction pathway for the N-formylation reaction, the time course of the initial period of the N-formylation of piperidine with triethylsilane (Et 3 SiH) using Cu(OAc) 2 $H 2 O and a diphosphine ligand, 1,2-bis(diisopropylphosphino)benzene (Chart 1, 1), was investigated.…”

“…1,2 Recently, the use of hydrosilanes as a reducing agent for CO 2 has received much attention because of the mild reaction conditions and diverse substrate scope. 3,4 In 2013, we reported the N-formylation of amines with 1 atm of CO 2 in the presence of a hydrosilane, polymethylhydrosiloxane (PMHS), a catalytic amount of Cu(OAc) 2 $H 2 O, and a diphosphine ligand (Scheme 1). 5 The turnover number exceeded 10,000.…”

A recyclable CO surrogate in regioselective alkoxycarbonylation of alkenes: indirect use of carbon dioxide

“…Therefore, we chose Rh--catalysed CO 2 hydrosilylation under mild conditions as a basis for our efforts. 16 Thus, silyl formate 9 was prepared following the literature procedure and it was subsequently converted to the anhydride 10 quantitatively at 40 °C. This mixture was then employed to synthesize 1 under the aforementioned conditions, albeit in somewhat lower yields possibly due to the presence of PhMe 2 SiOAc.…”

Efficient Conversion of Carbon Dioxide with Si‐Based Reducing Agents Catalyzed by Metal Complexes and Salts

“…(2)). Several reaction systems have been reported for the conversion of dimethylamine to DMF and various amines with functional groups to the corresponding formylation product with CO 2 and hydrosilane or H 2 using metal complexes or organocatalysts. The excellent catalytic performance of the Cu‐bisphosphine complex for hydrosilylation of CO 2 inspired us to examine its catalytic potential for the formylation of amines with CO 2 and hydrosilane.…”