Chiral Ligands for Rhodium‐Catalyzed Asymmetric Hydroformylation: A Personal Account

Chen, Caiyou; Dong, Xiu‐Qin; Zhang, Xumu

doi:10.1002/tcr.201600055

Cited by 19 publications

(3 citation statements)

References 49 publications

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“…Hydroformylation allows atom-efficient and direct formation of aldehydes from olefins and synthesis gas, and has become a powerful synthetic route for the preparation of some key organic intermediates [1]. Recently, hydroformylation of functionalized olefins has received considerable attention [2], especially in the aspect of some special olefins, cycloolefins [3], vinyl acetate [4][5][6], dicyclopentadiene (DCPD) [7,8] and 1,3-Butadiene [9]. Because their aldehyde products, especially linear products, can be used to prepare of a variety of biologically active compounds and fine chemicals, such as chiral alcohols, acids, amines, diols, and amino alcohols [10,11].…”

Section: Introductionmentioning

confidence: 99%

“…At present, hydroformylation is the largest application of homogeneous catalysis on an industrial scale with a capacity of more than 10 million tons per year, and is almost exclusively targeted to the production of the linear aldehydes [12]. However, for hydroformylation of vinyl acetate, the selectivity of linear aldehyde (3-acetoxy propanal) is mostly less than 5% among the existing reports [4][5][6].…”

Section: Introductionmentioning

confidence: 99%

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Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination

Chen

Liu

et al. 2019

Catalysts

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A simple and practical Rh-catalyzed hydroformylation of vinyl acetate has been synthesized via impregnation-calcination method using silicate nanotubes (MgSNTs) as the supporter. The Rh0 (zero valent state of rhodium) was obtained by calcination. The influence of calcination temperature on catalytic performance of the catalysts was investigated in detail. The catalysts were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectrometer (XPS), atomic emission spectrometer (ICP), and Brunauer–Emmett–Teller (BET) surface-area analyzers. The Rh/MgSNTs(a2) catalyst shows excellent catalytic activity, selectivity and superior cyclicity. The catalyst could be easily recovered by phase separation and was used up to four times.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination

Chen

Liu

et al. 2019

Catalysts

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“…The need for efficient AHF protocols served as an impetus to designing various catalysts suitable for this purpose. Rhodium complexes with chiral phosphorus-based ligands have emerged as a promising family of catalysts . The repertoire of phosphorus ligands such as Binaphos, Bis-diazophos, Chiraphite, Ph-BPE, YanPhos, and others found successful applications in AHF with a wide array of substrates.…”

Section: Introductionmentioning

confidence: 99%

Unraveling the Importance of Noncovalent Interactions in Asymmetric Hydroformylation Reactions

2020

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For catalytic asymmetric hydroformylation (AHF) of alkenes to chiral aldehydes, though a topic of high interest, the contemporary developments remain largely empirical owing to rather limited molecular insights on the origin of enantioselectivity. Given this gap, herein, we present the mechanistic details of Rh-(S,S)-YanPhoscatalyzed AHF of α-methylstyrene, as obtained through a comprehensive DFT (ω-B97XD and M06) study. The challenges with the double axially chiral YanPhos, bearing an N-benzyl BINOL-phosphoramidite and a BINAP-bis(3,5-t-Bu-aryl)phosphine, are addressed through exhaustive conformational sampling. The C−H•••π, π•••π, and lone pair•••π noncovalent interactions (NCIs) between the N-benzyl and the rest of the chiral ligand limit the N-benzyl conformers. Similarly, the C−H•••π and π•••π NCIs between the chiral catalyst and α-methylstyrene render the siface binding to the Rh-center more preferred over the re-face. The transition state (TS) for the regiocontrolling migratory insertion, triggered by the Rh-hydride addition to the alkene, to the more substituted α-carbon is 3.6 kcal/mol lower than that to the β-carbon, thus favoring the linear chiral aldehyde over the achiral branched alternative. In the linear pathway, the TS for the hydride addition to the si-face is 1.5 kcal/mol lower than that to the re-face, with a predicted ee of 85% for the S aldehyde (expt. 87%). The energetic span analysis reveals the reductive elimination as the turnover determining step for the preferred S linear aldehyde. These molecular insights could become valuable for exploiting AHF reactions for substituted alkenes and for eventual industrial implementation.

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Introduction to Aqueous Organometallic Chemistry and Catalysis

Ounkham

Frost

2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Aqueous‐phase organometallic chemistry is an important yet still underexplored area of chemistry and catalysis. An important aspect of organometallic chemistry in water is the potential to utilize the benefits of homogeneous catalysis (selectivity, activity, etc.) and couple that with the benefits of heterogeneous catalysis (ease of separation). Organometallic complexes can be made soluble in water through the use of various water‐soluble ligands. An overview of the unique characteristics of water with respect to organometallic complexes and reactivity are discussed including pH effects, hydrogen bonding, salt effects, and metal‐carbon bond stability. An introduction to the various types of ligands utilized in water‐soluble organometallic chemistry is provided. The most prevalent water‐soluble ligands are phosphines designed with polar or hydrophilic functional groups. Amines, ammonium salts, functionalized NHCs, and derivatives of cyclopentadiene or arenes are some of the other ligands that have been utilized in aqueous‐phase organometallic chemistry and catalysis. Water also makes a good ligand for some water‐soluble organometallic complexes and the reactivity of coordinated water can play a significant role in reactivity and/or catalysis. An introduction to the behavior of metal hydride ligands in aqueous environments is also presented. Finally, selected catalytic reactions carried out in aqueous media are discussed including hydrogenation, hydration, CC bond forming reactions, oxidation, hydroformylation, and olefin metathesis.

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Chiral Ligands for Rhodium‐Catalyzed Asymmetric Hydroformylation: A Personal Account

Cited by 19 publications

References 49 publications

Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination

Preparation and Characterization of Rh/MgSNTs Catalyst for Hydroformylation of Vinyl Acetate: The Rh0 was Obtained by Calcination

Unraveling the Importance of Noncovalent Interactions in Asymmetric Hydroformylation Reactions

Introduction to Aqueous Organometallic Chemistry and Catalysis

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