Practical synthesis of (S)-2-(4-fluorophenyl)-3-methylbutanoic acid, key building block for the calcium antagonist Mibefradil

Crameri, Yvo; Foricher, Joseph; Scalone, Michelangelo; Schmid, Rudolf

doi:10.1016/s0957-4166(97)00498-9

Cited by 35 publications

(22 citation statements)

References 21 publications

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“…[29] Similarly, Crameri et al [30] established that the hydrogenation of a,b-unsaturated acids using RuA C H T U N G T R E N N U N G (OAc) 2 {(R)-MeOBIPHEP} in the presence of NEt 3 increased both conversion and enantioselectivity. Such base addition presumably favours the formation of the active (hydride-containing) hydrogenation catalyst.…”

Section: Asymmetric Hydrogenation Of 2amentioning

confidence: 98%

β‐Hydroxycarboxylic Acids from Simple Ketones by Carboxylation and Asymmetric Hydrogenation

2008

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We present a new asymmetric synthesis of b-hydroxycarboxylic acids from ketones, performed by carboxylation using CO 2 followed by asymmetric hydrogenation. First, the carboxylation of ketones gives b-ketocarboxylic acids. The effects of temperature, reaction time, and amount of 1,.0]undec-7-ene (DBU) promoter on the carboxylation were investigated. The DBU can be recycled. For the second step, the asymmetric hydrogenation of these b-ketocarboxylic acids, we determined the effect of solvent choice, H 2 pressure, and substrate substitution. Hydrogenation yield and enantioselectivity are solvent-dependent, and the mechanism could proceed through hydrogenation of either the enol or the keto forms of the bound substrate. This synthesis is industrially advantageous due to the limited number of reactants required, their low-cost, and the potential for recycling unused materials.

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Section: Asymmetric Hydrogenation Of 2amentioning

confidence: 98%

β‐Hydroxycarboxylic Acids from Simple Ketones by Carboxylation and Asymmetric Hydrogenation

2008

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“…of 8-27%. The biotransformation has been demonstrated [28,29] useful for the preparation of enantiopure S-2-(4-fluorophenyl)-3-methylbatyric acid and S-2-(4-chlorophenyl)-3-methylbutyric acid (figure 1), which have been utilized, respectively, as a key intermediate for the calcium antagonist Mibefradil [30] and as a building block for pyrethroid [31].…”

Section: Enantioselective Biotransformations Of Racemic Nitrilesmentioning

confidence: 99%

Enantioselective Biotransformations of Nitriles in Organic Synthesis

Wang

2005

Top Catal

129

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Recent advances in enantioselective biotransformations of nitriles utilizing nitrile-hydrolyzing microorganisms and enzymes are summarized in this article. Various examples of biocatalytic synthesis of highly enantiopure carboxylic acids including amino acids, hydroxyl acids, cyclopropanecarboxylic acids and amide derivatives and oxiranecarboxamides are presented. The enantioselectivity of the nitrile hydratases, nitrilases and amideses is discussed.

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“…A key intermediate ( S ) -2 -(4 -fl uorophenyl) -3 -methylbutanoic acid for the synthesis of calcium antagonist Mibefradil was prepared in 94% ee through hydrogenation of the corresponding unsaturated acid using an ( R ) -BIPHEMP -Ru catalyst (Eq. 7.11 ) [199] . Using Rh -( R ) -47 as catalyst, the asymmetric hydrogenation of tert -butylammonium ( Z ) -3 -cyano -5 -methyl -3 -hexenoate led to the precursor to CI -1008 (pregabalin), a compound for psychotic disorder, seizure disorder, and pain.…”

Section: Unsaturated Acids and Their Derivativesmentioning

confidence: 99%

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

Gao

Zhang

2010

Catalytic Asymmetric Synthesis

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INTRODUCTIONAmong all the catalytic asymmetric methodologies to chiral compounds, homogenous transition metal -catalyzed asymmetric hydrogenation plays a particularly important role [1] . Its highly effi cient, environmental friendly, and cost -effective natures have undoubtly made it one of the most studied methodologies during the past 40 years. As a result, the vast number of catalytic systems developed has also had a signifi cant impact on other areas of asymmetric catalysis [2] . More signifi cantly, the achievements from academia research on asymmetric hydrogenation were frequently acknowledged with industrial applications, which, in turn, provide an important driving force for its basic research [3] .Hundreds of catalytic systems have been developed since the seminal discoveries from Knowles and Sabacky [4] , Kagan and Dang [5] , and Horner et al. [6] . In many cases, series of chiral catalysts were developed based on the similar scaffolds and were prepared for the same reactions. Although these analogous ligands are more likely prepared for the purpose of patent protection other than academic curiosity, they indeed provide us an excellent opportunity to compare, evaluate, and study every aspect of the catalysts in asymmetric hydrogenation. In the meantime, a large number of prochiral unsaturated compounds have been successfully hydrogenated with excellent enantioselectivities. Practical applications with very low catalyst loadings and complex substrate structures have continued to emerge since the publication of the last edition of this book.

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Practical synthesis of (S)-2-(4-fluorophenyl)-3-methylbutanoic acid, key building block for the calcium antagonist Mibefradil

Cited by 35 publications

References 21 publications

β‐Hydroxycarboxylic Acids from Simple Ketones by Carboxylation and Asymmetric Hydrogenation

β‐Hydroxycarboxylic Acids from Simple Ketones by Carboxylation and Asymmetric Hydrogenation

Enantioselective Biotransformations of Nitriles in Organic Synthesis

Transition Metal‐Catalyzed Homogeneous Asymmetric Hydrogenation

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