Reduction of Functionalized Alkenes

Genêt, Jean‐Pierre

doi:10.1002/9783527622115.ch1

Cited by 10 publications

(11 citation statements)

References 130 publications

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“…Asymmetric hydrogenation of prochiral CC bonds catalyzed by a transition metal is a useful methodology not only in academia but also at industrial scale. 340,341 Based on the models of Knowles, Kagan, and Noyori, homogeneous hydrogenation of olefins is performed mainly by Rh, Ru, and Ir complexes using chiral phosphorus ligands and has been the driving force for the development of asymmetric metal catalysis.…”

Section: Chemical Reviewsmentioning

confidence: 99%

Stereodivergent Catalysis

2018

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This review covers diastereo- and enantiodivergent catalyzed reactions in acyclic and cyclic systems using metal complexes or organocatalysts. Among them, nucleophilic addition to carbon-carbon and carbon-nitrogen double bonds, α-functionalization of carbonyl compounds, allylic substitutions, and ring opening of oxiranes and aziridines are considered. The diastereodivergent synthesis of alkenes from alkynes is also included. Finally, stereodivergent intramolecular and intermolecular cycloadditions and other cyclizations are also reported.

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Section: Chemical Reviewsmentioning

confidence: 99%

Stereodivergent Catalysis

2018

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“…[125][126][127][128] The high enantioselectivity (>90% ee) of this process usually relies on the availability of coordinating moieties in the substrate molecules (e.g., alcoholmoiety or carbonyl groups of esters, amides, etc.). 129 A collaboration of functional groups with the CÀ À C p-bond of olefin enables chelate ring formation that is pivotal in directing the stereochemistry of the hydrogenation process. 130,131 A wide variety of chiral Rh-complexes has been employed for C À ÀC bond asymmetric hydrogenation of numerous unsaturated substrates such as dehydro amido acids, enamides, allylic alcohols, enol esters, a,b-unsaturated acids, carbamates, and so on, giving an opportunity to synthesize chiral compounds with the interesting structural features of many biologically active and pharmaceutically important compounds.…”

Section: Rhodium-catalyzed Stereoselective Hydrogenation Of Functionamentioning

confidence: 99%

“…192 4-Methoxydalbergiones are natural urease inhibitors, 193 possessing antibacterial and antiplasmodial activity, 194,195 and they have been isolated from Dalbergia cochinchinensis (Laos Rosewood, Thai Rosewood, Cochin Rosewood) and Machaerium species together with other neoflavanoides, like dalbergichinoles and dalbergines. 196 Dalbergion is an interesting example of the simultaneous natural occurrence of structurally 129 130 SCHEME 29.5. Enantioselective synthesis of (S)-tolterodine via asymmetric hydrogenation.…”

Section: Rhodium-catalyzed Stereoselective Hydrogenation Of Functionamentioning

confidence: 99%

Stereoselective Hydrogenation ofCCBonds: Application to Drug and Natural Product Synthesis

Andrushko

2013

Stereoselective Synthesis of Drugs and Natural Products

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Asymmetric homogeneous hydrogenation is perhaps one of the most researched areas in homogeneous catalysis; thus, it is now used in numerous innovative applications in stereoselective syntheses of many chiral pharmaceutical and natural products. Metal complexes, derived from transition metals, like Rh, Ru, Ir, and so on, and chiral ligands (usually mono‐ or diphosphine ligands), are widely used as catalysts in asymmetric alkene hydrogenation as a result of their efficiency in the preparation of enantiopure compounds with excellent atom economy. This chapter provides many interesting examples of homogeneous enantio‐ and diastereoselective hydrogenation of CC bonds, highlighting the utility of these methods as useful synthetic tools for the construction of stereogenic centers in stereoselective drug and natural product syntheses.

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“…We immediately recognized that both the stereoselective synthesis of the tetra substituted cinnamate esters and the subsequent asymmetric hydrogenation would pose substantial challenges, particularly in the presence of the hydrogenation labile cyclopropyl substituents . Even though recent progress has been made in the asymmetric hydrogenation of tetra substituted enamides, α-dehydroamino acid derivatives, β-dehydroamino acid derivatives, and unsaturated carboxylic acids; fewer examples can be found around the asymmetric hydrogenation of unsaturated esters, enones and unfunctionalized olefins lacking strong coordinating functional groups.…”

Section: Introductionmentioning

confidence: 99%

Enantioselective Synthesis of α-Methyl-β-cyclopropyldihydrocinnamates

et al. 2016

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α- and β-substitution of dihydrocinnamates has been shown to increase the biological activity of various drug candidates. Recently, we identified enantio- and diastereopure α-methyl-β-cyclopropyldihydrocinnamates to be important pharmacophores in one of our drug discovery programs and endeavored to devise an asymmetric hydrogenation strategy to improve access to this valuable framework. We used high throughput experimentation to define stereoconvergent Suzuki-Miyaura cross-coupling conditions affording (Z)-α-methyl-β-cyclopropylcinnamates and subsequent ruthenium-catalyzed asymmetric hydrogenation conditions affording the desired products in excellent enantio- and diastereoselectivities. These conditions were executed on multigram to kilogram scale to provide three key enantiopure α-methyl-β-cyclopropyldihydrocinnamates with high selectivity.

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Reduction of Functionalized Alkenes

Cited by 10 publications

References 130 publications

Stereodivergent Catalysis

Stereodivergent Catalysis

Stereoselective Hydrogenation ofCCBonds: Application to Drug and Natural Product Synthesis

Enantioselective Synthesis of α-Methyl-β-cyclopropyldihydrocinnamates

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