A Highly Enantioselective Alkene Methoxycarbonylation Enables a Concise Synthesis of (<i>S</i>)‐Flurbiprofen

Harkness, Gavin J.; Clarke, Matthew L.

doi:10.1002/ejoc.201700791

Cited by 29 publications

(22 citation statements)

References 60 publications

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“…Another olefin transformation reaction where palladium complexes have gained much prominence is the methoxycarbonylation of olefins . Methoxycarbonylation of olefins is an attractive industrial synthetic strategy due to the inherent production of useful commodities such as pharmaceuticals, perfumes, surfactants and fragrances . Traditionally, phosphine‐based palladium complexes have been used in these reactions and still remain the most superior catalysts .…”

Section: Introductionmentioning

confidence: 99%

Structural and theoretical studies of the methoxycarbonylation of higher olefins catalysed by (Pyrazolyl‐ethyl)pyridine palladium (II) complexes

Zulu

Alam

Ojwach

et al. 2019

Applied Organom Chemis

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Reactions of 2-[1-(3,5-dimethylpyrazol-1-yl)ethyl]pyridine (L1) and 2-[1-(3,5diphenylpyrazol-1-yl)ethyl]pyridine (L2) with the [Pd (COD)Cl 2 ] or [Pd (COD)MeCl] produced palladium (II) complexes [Pd(L1)ClMe] (1), [Pd(L1) Cl 2 ] (C2), [Pd(L2)ClMe] (3), and [Pd(L2)Cl 2 ] (4) in quantitative yields. Solid state structures of complexes 1, 3 and 4 established the formation of mononuclear compounds, containing one bidentate ligand unit per metal atom, to give square planar complexes. All the other spectroscopic characterization data and elemental analyses were consistent with the observed structures. All the palladium (II) complexes 1-4 gave active catalysts in the methoxycarbonylation of 1-octenes. The catalysts demonstrated 100% chemoselectivities towards esters and favored the formation of linear isomers. Reaction conditions such as the type of phosphine derivative, acid promoter, solvent system, time, pressure and temperature have been investigated and shown to affect both the catalytic activity and regio-selectivity of the catalysts. Solid-angle modelling established the comparable steric contributions from the ligands, consistent with the similar regioselectivities of the resultant catalysts.

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Section: Introductionmentioning

confidence: 99%

Structural and theoretical studies of the methoxycarbonylation of higher olefins catalysed by (Pyrazolyl‐ethyl)pyridine palladium (II) complexes

Zulu

Alam

Ojwach

et al. 2019

Applied Organom Chemis

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“…catalyst ((S)-2-2mo) was used in a two-step synthesis of (S)flurbiprofen methyl ester from commercially available 4bromo-2-fluoro-1,1′-biphenyl [8]. The reaction mechanism of this Pd/Phanephos-catalyzed methoxycarbonylation of styrene was investigated based on density functional theory (DFT) computations supported by the results of deuterium labeling studies [9].…”

Section: Palladium-catalyzed Intermolecular Hydroalkoxycarbonylationsmentioning

confidence: 99%

Palladium-catalyzed enantioselective carbonylation reactions

Peng

Liu

et al. 2022

Sci. China Chem.

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Carbonylation, one of the most powerful approaches to the preparation of carbonylated compounds, has received significant attention from researchers active in various fields. Indeed, impressive progress has been made on this subject over the past few decades. Among the various types of carbonylation reactions, asymmetric carbonylation is a straightforward methodology for constructing chiral compounds. Although rhodium-catalyzed enantioselective hydroformylations have been discussed in several elegant reviews, a general review on palladium-catalyzed asymmetric carbonylations is still missing. In this review, we summarize and discuss recent achievements in palladium-catalyzed asymmetric carbonylation reactions. Notably, this review’s contents are categorized by reaction type.

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“…Likewise,naproxen (13)w as obtained in 85 %y ield from 3y under similar reaction conditions.T otest the practicality of this asymmetric cross-coupling,the reaction of 1e and 2r was studied on gram scale in the presence of Pd(OAc) 2 (0.5 mol %) and L11 (0.6 mol %), and the desired product 3r was obtained in 52 % yield and 89 %ee. Acidic treatment of 3rled to the formation of (R)-flurbiprofen [15] in 89 %ee.…”

Section: Angewandte Chemiementioning

confidence: 99%

Enantioselective Palladium‐Catalyzed Cross‐Coupling of α‐Bromo Carboxamides and Aryl Boronic Acids

Aliyu

et al. 2019

Angew Chem Int Ed

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A Highly Enantioselective Alkene Methoxycarbonylation Enables a Concise Synthesis of (S)‐Flurbiprofen

Cited by 29 publications

References 60 publications

Structural and theoretical studies of the methoxycarbonylation of higher olefins catalysed by (Pyrazolyl‐ethyl)pyridine palladium (II) complexes

Structural and theoretical studies of the methoxycarbonylation of higher olefins catalysed by (Pyrazolyl‐ethyl)pyridine palladium (II) complexes

Palladium-catalyzed enantioselective carbonylation reactions

Enantioselective Palladium‐Catalyzed Cross‐Coupling of α‐Bromo Carboxamides and Aryl Boronic Acids

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