ChemInform Abstract: Highly Enantioselective Hydroformylation of Olefins Catalyzed by New Phosphinephosphite‐Rh(I) Complexes.

Sakai, Nozomu; Mano, Satoshi; Nozaki, Kyoko; Takaya, Hidemasa

doi:10.1002/chin.199349055

Cited by 3 publications

(5 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, elaborate multistep syntheses frequently prevent application on industrial scale. One of the first ligands, (R,S)-BINAPHOS, with some potential for the manufacture of chiral fine chemicals was developed by Takaya and Nozaki almost 30 years ago [36].…”

Section: Ligands Designed For Industrial Applicationsmentioning

confidence: 99%

Hydroformylation

2021

View full text Add to dashboard Cite

Hydroformylation is one of the most important homogeneously catalyzed reactions on an industrial scale. The manufacture of bulk chemicals clearly dominates. Large cobalt- and rhodium-based processes are mature technologies that have been developed over the past 80 years. Meanwhile, the potential of hydroformylation for the production of fine chemicals (perfumes, pharmaceuticals) has also been recognized. This review gives insight into the state-of-the-art of the reaction and its development. It commences with some remarks on the accidental discovery by the German chemist Otto Roelen within the historical and personal framework of the Fischer–Tropsch process, followed by the mechanistic basics of the catalytic cycle, metals used for the catalyst as well as their organic ligands. In addition, the stability of ligands and catalysts is addressed. The huge potential of this transformation is demonstrated using a variety of substrates. Finally, the use of some surrogates for syngas is discussed.

show abstract

Section: Ligands Designed For Industrial Applicationsmentioning

confidence: 99%

Hydroformylation

2021

View full text Add to dashboard Cite

show abstract

“…In 1993, the most remarkable contribution in the field of asymmetric hydroformylation was reported by Takaya and coworkers 48 with the introduction of the BINAPHOS 4 the hybrid phosphine−phosphite ligands and ee up to 95% had been achieved for the asymmetric hydroformylation of styrene 1 while using Rh-Binaphos catalytic system (Figure 2).…”

Section: ■ Enantioselective Hydroformylationmentioning

confidence: 99%

“…55 It was obvious that a few ligands were capable to give enantioselectivities more than 90% during asymmetric hydroformylation and some reports had emphasized that mixed phosphorus ligands having two different phosphorus groups were efficient in such reactions. 48,56−58 Influenced by studies made by Takaya and co-workers 48 on the configuration matched for (R,S)-4a and (S,R)-4b Binaphos, phosphine− phosphoramidite analogue of Binaphos, (R,S-17) has been developed by Zhang et al, 59 taking chiral NOBIN (2-amino-2′-hydroxy-1,1′-binaphthyl) as a starting material. With Rhcatalyzed and (R,S)-17 as the ligand, extraordinary high enantioselectivities (ee up to 99%) had been achieved for asymmetric hydroformylation (Figure 5) and a significant improvement in the performance was observed as compared to the standard ligand, Binaphos.…”

Section: ■ Enantioselective Hydroformylationmentioning

confidence: 99%

“…With Rhcatalyzed and (R,S)-17 as the ligand, extraordinary high enantioselectivities (ee up to 99%) had been achieved for asymmetric hydroformylation (Figure 5) and a significant improvement in the performance was observed as compared to the standard ligand, Binaphos. 48 The high reactivity as well as excellent enantioselectivity with this novel ligand makes the catalytic system potentially suitable for industrial application in the preparation of optically pure 2-aryloxypropanoic acids.…”

Section: ■ Enantioselective Hydroformylationmentioning

confidence: 99%

See 1 more Smart Citation

Developments in the Catalytic Asymmetric Synthesis of Agrochemicals and Their Synthetic Importance

Sharma¹,

Paniraj²,

Tambe³

2021

J. Agric. Food Chem.

View full text Add to dashboard Cite

Catalytic asymmetric synthesis has become an essential tool for the enantioselective synthesis of pharmaceuticals, natural products, and agrochemicals (mainly fungicides, herbicides, insecticides, and pheromones). With continuous growing interest in both modern agricultural chemistry and catalytic asymmetric synthesis chemistry, this review provides a comprehensive overview of some earlier reports as well as the recent successful applications of various catalytic asymmetric syntheses methodologies, such as enantioselective hydroformylation, enantioselective hydrogenation, asymmetric Sharpless epoxidation and dihydroxylation, asymmetric cyclopropanation or isomerization, organocatalyzed asymmetric synthesis, and so forth, which have been used as key steps in the preparation of chiral agrochemicals (on R&D, piloting, and commercial scales). Chiral agrochemicals can also lead the new generation of such chemicals having specific and novel modes of action for achieving sustainable crop protection and production. Some perspectives and challenges for these catalytic asymmetric methodologies in the synthesis of chiral agrochemicals are also briefly discussed in the final section of the manuscript. This review will provide the insight regarding understanding, development, and evaluation of catalytic asymmetric systems for the synthesis of chiral agrochemicals among the agrochemists.

show abstract

“…In 1993, Nozaki and co -workers [39] combined an unsymmetrical phosphine -phosphite ligand, ( R,S ) -BINAPHOS, and a rhodium (I) catalyst to afford chiral aldehydes with excellent enantioselectivities from prochiral olefi ns. Since then, these catalysts, ( R,S ) -BINAPHOS -Rh(I) (acac), became (and still are) the most potent catalysts for asymmetric hydroformylation.…”

Section: Hydroformylationmentioning

confidence: 99%