Enantioselective Desymmetrizations of Diesters to Synthesize Fully Substituted Chiral Centers of 3,4‐Dihydrocoumarins and Related Compounds

Kelley, Amber M.; Haywood, Rhashanda D.; White, J. C.; Petersen, Kimberly S.

doi:10.1002/slct.202000312

Cited by 9 publications

(3 citation statements)

References 39 publications

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“…Although naturally occurring dihydrocoumarin concentrations are limited in plants, advances in organic synthesis technology have enabled the development of multiple methods for dihydrocoumarin production, including microbial biocatalysis from coumarin (Häser et al, 2006) and organic synthesis (Bojanowski et al, 2019;Kelley et al, 2020). It is therefore not difficult to obtain dihydrocoumarin in large quantities.…”

Section: Discussionmentioning

confidence: 99%

The potential of Myosoton aquaticum extracts and compounds to control barnyardgrass (Echinochloa crus‐galli)

et al. 2021

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Although cover crops are widely used for weed suppression in the agroecosystem, little research is available regarding the possibility that the decomposed weed solution may control weeds. In this study, we tested the allelopathic effect of decomposed weed solution on barnyardgrass (Echinochloa crus-galli). In two separate tests, we found that the solution of decomposed Myosoton aquaticum completely suppressed the germination of barnyardgrass seeds at a concentration of 20 g l-1. We then isolated and identified the predominant inhibitory substance in the decomposed M. aquaticum solution. The solution was subjected to organic solvent extraction and then separated on a silica gel column before the final identification of its components by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS). Dihydrocoumarin was isolated from the M2 and M3 fractions using a bioassayguided method and was found to be the most active of eleven candidate allelochemical compounds. Dihydrocoumarin is typically used as a food additive. In this study, barnyardgrass germination was completely inhibited when treated with dihydrocoumarin at 1 g l-1, and its root and shoot growth were significantly inhibited at an application rate of 0.005 g l-1. Dihydrocoumarin showed highly efficient inhibition of root and shoot growth in barnyardgrass at low concentrations compared with coumarin.These findings show that weeds may be used as cover crops to provide allelochemicals for weed suppression and that dihydrocoumarin has the potential to be used as a bioherbicide.

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Section: Discussionmentioning

confidence: 99%

The potential of Myosoton aquaticum extracts and compounds to control barnyardgrass (Echinochloa crus‐galli)

et al. 2021

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“…The elucidation of the relationship between chemical structures and their biological activities is one of the most important research topics for chemical scientists . Fragrance chemistry is one of the few domains where chemists can directly experience such structure–activity relationships (SARs) sensorily, simply by smelling .…”

Section: Introductionmentioning

confidence: 99%

Direct Oxidative Cyclization of 3-Arylpropionic Acids to 3,4-Dihydrocoumarins: Reinvestigation of the Reaction Mechanism

Zeng,

Ye,

Chai

et al. 2024

J. Org. Chem.

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Instigated by olfactory analysis of odorant molecules, the constitutions of 3,4-dihydrocoumarins prepared by PIFA-based oxidative cyclizations of 3-arylpropionic acids were revised by means of 2D NMR and X-ray analysis. Supported by computational analysis, the migratory mechanism of intermediate spirolactonic cations has been amended: 1,2-alkyl shifts instead of 1,2-carboxylic shifts were selectively obtained.

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“…In this work, we show that a suite of pipecolinol-derived tetradentate ligands can accommodate various types of nitrogen-/oxygen-substituted malonic esters to deliver the enantioenriched hydrosilylation products. While similar malonic esters have been desymmetrized before, these transformations were intramolecular and only chiral heterocycles were accessed in most cases 22 – 25 . In comparison, the reductive and intermolecular desymmetrization brings abundant application potential with the resulting β-hydroxyester motif and heteroatom substituents.…”

Section: Introductionmentioning

confidence: 99%

Diverse synthesis of α-tertiary amines and tertiary alcohols via desymmetric reduction of malonic esters

Liu

Lau

et al. 2022

Nat Commun

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Amines and alcohols with a fully substituted α-carbon are structures of great value in organic synthesis and drug discovery. While conventional methods towards these motifs often rely on enantioselective carbon-carbon or carbon-heteroatom bond formation reactions, a desymmetric method is developed here by selectively hydrosilylating one of the esters of easily accessible α-substituted α-amino- and -oxymalonic esters. The desymmetrization is enabled by a suite of dinuclear zinc catalysts with pipecolinol-derived tetradentate ligands and can accommodate a diverse panel of heteroatom substituents, including secondary amides, tertiary amines, and ethers of different sizes. The polyfunctionalized reduction products, in return, have provided expeditious approaches to enantioenriched nitrogen- and oxygen-containing molecules, including dipeptides, vitamin analogs, and natural metabolites.

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Enantioselective Desymmetrizations of Diesters to Synthesize Fully Substituted Chiral Centers of 3,4‐Dihydrocoumarins and Related Compounds

Cited by 9 publications

References 39 publications

The potential of Myosoton aquaticum extracts and compounds to control barnyardgrass (Echinochloa crus‐galli)

The potential of Myosoton aquaticum extracts and compounds to control barnyardgrass (Echinochloa crus‐galli)

Direct Oxidative Cyclization of 3-Arylpropionic Acids to 3,4-Dihydrocoumarins: Reinvestigation of the Reaction Mechanism

Diverse synthesis of α-tertiary amines and tertiary alcohols via desymmetric reduction of malonic esters

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