Transition metal-catalyzed branch-selective hydroformylation of olefins in organic synthesis

Ning, Yingtang; Ohwada, Tomohiko; Chen, Fen‐Er

doi:10.1016/j.gresc.2021.04.008

Cited by 49 publications

(28 citation statements)

References 182 publications

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“…Olefin isomerization is an atom-economical and synthetically useful transformation . Significant progress has been made in terms of substrate scope, catalytic efficiency, and site selectivity of these reactions . Despite all these achievements, only a handful of enantioselective examples have been reported to date .…”

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confidence: 99%

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

et al. 2021

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Chiral cyclic olefins, 1-methylcyclohexenes, are versatile building blocks for the synthesis of pharmaceuticals and natural products. Despite the prevalence of these structural motifs, the development of efficient synthetic methods remains an unmet challenge. Herein we report a novel desymmetric isomerization of exocyclic olefins using a series of newly designed chiral cobalt catalysts, which enables a straightforward construction of chiral 1-methylcyclohexenes with diversified functionalities. The synthetic utility of this methodology is highlighted by a concise and enantioselective synthesis of a natural product, β-bisabolene. The versatility of the reaction products is further demonstrated by multifarious derivatizations.

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confidence: 99%

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

et al. 2021

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“…It also circumvents another issue encountered in conventional cross-coupling, that the basic and nucleophilic nature of pregenerated organometallic reagents can often lead to limited functional-group compatibility, rendering it unable to handle sensitive functionality. Recently, nickel hydride − has proved to be an efficient catalyst for enantioselective reductive hydrofunctionalization, especially in hydroalkylation reactions (Figure a). In this process, chiral induction could occur in one of two possible steps: (i) enantioconvergent alkylation with racemic 2° or 3° alkyl halide to form enantioenriched Ni(III) intermediates, constructing stereocenter at the carbon originating from racemic electrophile; − or (ii) enantioselective syn -hydrometalation of NiH with an alkene to form enantioenriched alkylnickel species, constructing a stereocenter at the carbon originating from achiral olefin. − …”

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confidence: 99%

Catalytic Asymmetric Hydroalkylation of α,β-Unsaturated Amides Enabled by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation

Zhou

Zhu

2021

ACS Catal.

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Here, we report an enantioselective nickel-hydride catalyzed hydroalkylation of readily accessible β-alkyl-α,β-unsaturated amides to form structurally diverse β-chiral amides. This process was proposed to proceed through an enantiodifferentiating syn-hydrometalation of nickel hydride, forming chiral alkylnickel at the β-position in which the regioselectivity is different from that with copper hydride. This regio-reversed hydronickellation process provides a complementary approach to access enantioenriched β-functionalization amides with a stereocenter at the β-position.

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“…However, limited progress has been achieved thus far and no methods have been commercialized. The main approach has been the development of tailored phosphorus ligands of the Rh catalysts [5] . For instance, in a collaboration with Eastman Chemical Company (ECC), one of the leaders in industrial hydroformylation, Reek and colleagues reported that encapsulation of a Rh center inside of a capsule‐like tris‐Zn‐porphyrin‐tris(3‐pyridyl)phosphine inverted the reaction selectivity, reaching up to 1.2 : 1 iso / n ratio of products at 25 °C (Figure 1b) [13–15] .…”

Section: Figurementioning

confidence: 99%

“…Lastly, because the isoselective hydroformylation of simple aliphatic alkenes remains underdeveloped, [5] we investigated the performance of the Pd catalyst in such cases (Figure 7). Remarkably, terminal alkenes of different length, 1‐pentene to 1‐octene, reacted to form aldehydes in 92–95 % yields with 2.4 : 1–2.8 : 1 iso / n ratios and the selective formation of α‐methyl isomer among iso‐ aldehydes (70–86 % α‐selectivity).…”

Section: Figurementioning

confidence: 99%

Isoselective Hydroformylation of Propylene by Iodide‐Assisted Palladium Catalysis

et al. 2022

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Isobutanal is a high value bulk material that, in principle, could be produced with 100 % atomeconomy by isoselective hydroformylation of propylene with syngas. However, leading industrial Rh-and Cocatalyzed hydroformylation methods preferentially form n-butanal over the iso-product, and methods offering isoselectivity remain underdeveloped. Here we report an iodide-assisted Pd-catalyzed hydroformylation of propylene that produces isobutanal with unprecedented levels of selectivity. The method involves PdI 2 , simple alkyl monophosphines, such as tricyclohexylphosphine, and common green solvents, enabling the title reaction to occur with isoselectivity in up to 50 : 1 iso/n product ratios under industrially relevant conditions (80-120 °C). The catalytic and preliminary mechanistic experiments indicate a key role of the iodide anions in both the catalytic activity and the isoselectivity.

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Transition metal-catalyzed branch-selective hydroformylation of olefins in organic synthesis

Cited by 49 publications

References 182 publications

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Cobalt-Catalyzed Desymmetric Isomerization of Exocyclic Olefins

Catalytic Asymmetric Hydroalkylation of α,β-Unsaturated Amides Enabled by Regio-Reversed and Enantiodifferentiating syn-Hydronickellation

Isoselective Hydroformylation of Propylene by Iodide‐Assisted Palladium Catalysis

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