- Palladium-Catalyzed Reductive Conversion of Acyl Fluorides via Ligand-Controlled Decarbonylation
-
Ligand-controlled non-decarbonylative and decarbonylative conversions of acyl fluorides were developed using a Pd(OAc)2/Et3SiH combination. When tricyclohexylphosphine (PCy3) was used as the ligand, aldehydes were obtained as simple reductive conversion products. The use of 1,2-bis(dicyclohexylphosphino)ethane (Cy2P(CH2)2PCy2, DCPE) as the ligand, however, favored the formation of hydrocarbons, which are decarbonylative reduction products.
- Ogiwara, Yohei,Sakurai, Yuka,Hattori, Hiroyuki,Sakai, Norio
-
supporting information
p. 4204 - 4208
(2018/07/29)
-
- Selective switchable iron-catalyzed hydrosilylation of carboxylic acids
-
Selective reduction of carboxylic acids either to aldehydes or alcohols is achieved using a one pot procedure based on iron-catalyzed hydrosilylations. Using phenylsilane and (COD)Fe(CO)3 catalyst under UV-irradiation at rt, alcohols were obtained specifically in good yields, whereas aldehydes were selectively obtained using TMDS and (t-PBO)Fe(CO)3 catalyst under thermal activation.
- Misal Castro, Luis C.,Li, Haoquan,Sortais, Jean-Baptiste,Darcel, Christophe
-
supporting information
p. 10514 - 10516,3
(2020/09/02)
-
- Catalytic Asymmetric Epoxidations with Chiral Iron Porphyrins
-
Iron porphyrins have been modified to include optically active functionalities at the meso positions.Asymmetric epoxidations of prochiral olefins with these chiral iron porphyrins and iodosyl compounds have been investigated.Thus, 5α,10β,15α,20β-tetrakis(o-(R)-hydratropamidophenyl)porphyrin (H2T(α,β,α,β-Hyd)PP) and 5α,10β,15α,20β-tetrakis(ophenyl)porphyrin (H2T(α,β,α,β-Binap)PP) were synthesized by the condensation of optically active acid chlorides with 5α,10β,15α,20β-tetrakis(o-aminophenyl)porphyrin.Subsequent insertion of iron into H2T(α,β,α,β-Hyd)PP and H2T(α,β,α,β-Binap)PP gave FeT(α,β,α,β-Hyd)PPCl and FeT(α,β,α,β-Binap)PPCl, respectively.Emploing FeT(α,β,α,β-Hyd)PPCl iodosylbenzene, styrene was oxidized to (R)-(+)-styrene oxide in 31percent ee.Similarly, FeT(α,β,α,β-Binap)PPCl and iodosylmesitylene gave (R)-(+)-styrene oxide in 48percent ee.Various substituted styrenes and aliphatic olefins were epoxidized with enantiomeric excesses varying between 0percent for 1-methylcyclohexene oxide and 51percent for p-chlorostyrene oxide.
- Groves, John T.,Myers, Richard S.
-
p. 5791 - 5796
(2007/10/02)
-
