scholarly journals Recent Advances in Ru Catalyzed Transfer Hydrogenation and Its Future Perspectives

2021 ◽  
Author(s):  
Nidhi Tyagi ◽  
Gongutri Borah ◽  
Pitambar Patel ◽  
Danaboyina Ramaiah

Over the past few decades, Ru catalyzed transfer hydrogenation (TH) and asymmetric transfer hydrogenation (ATH) reactions of unsaturated hydrocarbons, imine, nitro and carbonyl compounds have emerged as economic and powerful tools in organic synthesis. These reactions are most preferred processes having applications in the synthesis of fine chemicals to pharmaceuticals due to safe handling as these do not require hazardous pressurized H2 gas. The catalytic activity and selectivity of Ru complexes were investigated with a variety of ligands based on pincer NHC, cyclophane, half-sandwich, organophosphine etc. These ligands coordinate to Ru center in a proper orientation with a labile group replaced by H-source (like methanol, isopropanol, formic acid, dioxane, THF), which facilitate the β-hydrogen transfer to generate metal hydride species (Ru-H) and produce desired reduced product. This chapter describes the recent advances in TH and ATH reactions with homogeneous and heterogeneous Ru catalysts having different ligand environments and mechanistic details leading to their sustainable industrial applications.

Molecules ◽  
2021 ◽  
Vol 26 (4) ◽  
pp. 1165
Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2′-bis(aminomethyl)-1,1′-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = η5–C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium complexes (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to a catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to an enantiomeric excess (ee) of 67%.


Author(s):  
Yasuhiro Sato ◽  
Yuichi Kawata ◽  
Shungo Yasui ◽  
Yoshihito Kayaki ◽  
Takao Ikariya

As a candidate for bifunctional asymmetric catalysts containing a half-sandwich C–N chelating Ir(III) framework (azairidacycle), a dinuclear Ir complex with an axially chiral linkage is newly designed. An expedient synthesis of chiral 2,2’-bis(aminomethyl)-1,1’-binaphthyl (1) from 1,1-bi-2-naphthol (BINOL) was accomplished by a three-step process involving nickel-catalyzed cyanation and subsequent reduction with Raney-Ni and KBH4. The reaction of (S)-1 with an equimolar amount of [IrCl2Cp*]2 (Cp* = 5-C5(CH3)5) in the presence of sodium acetate in acetonitrile at 80 °C gave a diastereomeric mixture of new dinuclear dichloridodiiridium (5) through the double C–H bond cleavage, as confirmed by 1H NMR spectroscopy. A loss of the central chirality on the Ir centers of 5 was demonstrated by treatment with KOC(CH3)3 to generate the corresponding 16e amidoiridium complex 6. The following hydrogen transfer from 2-propanol to 6 provided diastereomers of hydrido(amine)iridium with retaining the bis(azairidacycle) architecture. The dinuclear chlorido(amine)iridium 5 can serve as a catalyst precursor for the asymmetric transfer hydrogenation of acetophenone with a substrate to catalyst ratio of 200 in the presence of KOC(CH3)3 in 2-propanol, leading to (S)-1-phenylethanol with up to 67% ee.


2012 ◽  
Vol 1 (3) ◽  
pp. 155-163 ◽  
Author(s):  
Maya Shankar Singh

2020 ◽  
Vol 09 ◽  
Author(s):  
C M A Afsina ◽  
Mohan Neetha ◽  
Thaipparambil Aneeja ◽  
Gopinathan Anilkumar

: Furan and its derivatives find wide-spread application as pharmaceuticals, pigments, dyes, brighteners, flavour & fragrance compounds and insecticides. They also exhibit anti-hyperglycemic, analgesic, anti-inflammatory, antibacterial, anti-fungal and anti-tumour activities. Silver catalysts are nowadays commonly used in organic synthesis due to the high oxidation potential and versatile nature of silver complexes. In this review, we summarise the recent advances in the synthesis and applications of furan moiety using silver catalysis and covers literature from 2015-2020.


2021 ◽  
Vol 17 ◽  
pp. 100264
Author(s):  
Vicky Subhash Telang ◽  
Rakesh Pemmada ◽  
Vinoy Thomas ◽  
Seeram Ramakrishna ◽  
Puneet Tandon ◽  
...  

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