Highly Regioselective Hydroformylation of Styrene and Its Derivatives Catalyzed by Rh Complex with Tetraphosphorus Ligands

Yu, Shichao; Chie, Yu-ming; Zhang, Guan; Zou, Yaping; Li, Wei; Zhang, Xumu

doi:10.1021/ol802479y

Cited by 72 publications

(40 citation statements)

References 44 publications

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“…The electron-withdrawing properties of the pyrrolyl group give the ligand good p-accepting ability, which is favorable for linear aldehyde regioselectivity in either linear olefin or styrene hydroformylation. [9,17,22,23] Therefore, the relatively higher selectivity and activity caused by ligand 1 were attributed to the presence of electron-withdrawing pyrrolyl group. Analogously, it can be seen that ligand 4 containing the pyrrolyl group exhibited a higher L/B ratio than ligand 5.…”

Section: Resultsmentioning

confidence: 99%

“…Zhang et al also revealed this phenomenon when they used ligand (III) in the Rh-catalyzed aryl alkene hydroformylation. [9] It is worth noting that the steric hindrance of the substrates remarkably influences the regioselectivity. [9] In our case, when a-methylstyrene was used as the substrate, few branched aldehydes were yielded (Table 3, entry 4), but the reaction rate decreased obviously.…”

Section: Resultsmentioning

confidence: 99%

“…[5,6] The fact that the linear aldehyde has significant application potential caused researchers to investigate the hydroformylation of styrene more thoroughly. [7][8][9] Recently, by using some specific ligands, linear aldehyde selectivity for the hydroformylation of styrene has increased. For instance, Van Leeuwen's Xantphos derivatives (I) gave an L/B (molar ratio of linear to branched aldehyde) ratio of 2.35 for styrene hydroformylation.…”

Section: Introductionmentioning

confidence: 99%

“…[7] Sémeril and co-workers' calixarene-based diphosphites (II) led an L/B ratio of up to 12.4. [8] Zhang et al developed a tetraphosphorus ligand (III) for styrene hydroformylation with an L/B ratio of 22 [9] (Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

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Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

Zheng

Mo²,

Liang

et al. 2013

Applied Organom Chemis

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Different kinds of mono-and bidentate phosphite ligands were used in Rh-catalyzed hydroformylation of styrene to illustrate the influence of steric and electronic properties of ligands on catalytic performance. High activity (99.9%) and good regioselectivity (85.4%) to the linear aldehyde were achieved under optimum conditions in the presence of Rh/bisphosphite complex (bisphosphite: 2,2 0 -bis(dipyrrolylphosphinooxy)-1,1 0 -(AE)-binaphthyl). This system makes it possible to prepare functionalized terminal aldehydes from readily available styrene or its derivatives through hydroformylation with high linear selectivity.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

Zheng

Mo²,

Liang

et al. 2013

Applied Organom Chemis

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“…The 1,4-addition of benzene derivatives to acrolein is a onestep aromatic substitution reaction to generate 3-arylpropanals as compared with the other routes, such as (a) oxidation of 3-arylpropan-1-ol, 10 (b) selective hydrogenation of cinnamyl aldehydes, 11 (c) hydroformylation of styrenes, 12 (d) arylation of allylic alcohols followed by isomerization, 13 and (e) hydrosilylation of cyclic malonates 14 (Scheme 1). The previous 1,4-addition of benzene derivatives to acrolein has been found only in the following three articles, indicating a limited substrate scope for the reaction: Alkyl-substituted benzenes, such as toluene, cumene, and tert-butylbenzene, added to acrolein using a stoichiometric amount of TiCl 4 , in up to a 38% yield (Scheme 2a).…”

Section: Introductionmentioning

confidence: 99%

H-type Zeolite-Catalyzed 1,4-Addition of Benzene Derivatives to Labile Acrolein

Hayashi

Narisawa

Masui

et al. 2016

Bulletin of the Chemical Society of Japan

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The 1,4-addition of benzene derivatives to acrolein is a straightforward way to synthesize 3-arylpropanals. A survey of acid catalysts for the 1,4-addition of methoxy-substituted benzenes to acrolein revealed that H-Beta and H-Y were the most suitable catalysts. We hypothesized three side-reactions: (1) the double 1,4-addition of acrolein to the starting benzene derivatives, (2) the FriedelCrafts-type alkylation to the desired product, and (3) the self-polymerization of acrolein. The type (3) side-reaction was inhibited by two different methods which kept the concentration of acrolein low in the reaction mixture or in the zeolite pores. First, acrolein monomers were in situ generated through the gradual monomerization of an acrolein cyclic trimer. Second, using a reaction solvent lowered the acrolein concentration in the zeolite pores due to the competitive adsorption. We discovered that the content of monomeric acrolein in a solvent was closely related to the polarity of the solvent. Actually, both methods improved the yields for the 1,4-additions of 1,3-dimethoxybenzene to acrolein. Other electronrich benzene derivatives, such as phenol and N,N-dimethylaniline, were also applicable to the 1,4-addition reactions.

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Enantioselective Hydroformylation

2021

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Hydroformylation is powerful catalytic reaction capable of converting alkenes directly into aldehydes by addition of a formyl group and hydrogen across the double bond. Installation of the formyl group at an internal carbon establishes a chiral center, and a variety of chiral ligands may be employed to direct the enantioselectivity of the reaction. The alkene substrates are easily accessed, and the resultant aldehydes are common precursors for diverse synthetic manipulations. This chapter covers enantioselective hydroformylation from its inception, presents the most common metal precursors and ligands, and includes all examples that produce aldehydes with yields above 20% and enantioselectivity above 60:40 er. The initial discussion focuses on the mechanism and stereochemistry, and on the regio‐ and enantioselectivity‐determining steps in particular, as these are crucial for overall yield. The “Scope and Limitations” section is divided by substrate type and offers examples of exceptional catalytic systems that have been reported for each. The application of enantioselective hydroformylation to synthetic procedures is discussed by highlighting some reported examples, comparing it to other protocols that also afford chiral aldehydes, and exploring the standard experimental conditions. The intention of this review is to demonstrate the power and scope of enantioselective hydroformylation to researchers, and to provide a suitable starting point for those interested in its application to their own synthetic strategies.

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Highly Regioselective Hydroformylation of Styrene and Its Derivatives Catalyzed by Rh Complex with Tetraphosphorus Ligands

Cited by 72 publications

References 44 publications

Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

Rhodium/bisphosphite catalytic system for hydroformylation of styrene and its derivatives

H-type Zeolite-Catalyzed 1,4-Addition of Benzene Derivatives to Labile Acrolein

Enantioselective Hydroformylation

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