Synthesis of α-Functionalized and Nonfunctionalized Hydroximoyl Chlorides from Conjugated Nitroalkenes and Nitroalkanes

Kumaran, Govindaraj; Kulkarni, G. H.

doi:10.1021/jo961553o

Cited by 48 publications

(13 citation statements)

References 56 publications

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“…The asymmetric cyanation of activated olefins such as α,β‐unsaturated ketones4 α,β‐unsaturated imides,5 α,β‐unsaturated N ‐acylpyrroles,6 α,β‐unsaturated esters,7 carbohydrate‐derived nitroolefins,8 and nitroalkenes are little studied compared to the asymmetric cyanation of CO and CN9 bonds. Moreover, β‐nitronitriles can also be synthesized from hydrazone‐derived substrates10 and conjugated nitroalkenes 11. As a result of the strong tendency of nitroalkenes to polymerize in a basic medium, there are only four examples of asymmetric cyanide addition to nitroolefins in the literature to date 1.…”

Section: Introductionmentioning

confidence: 99%

An Evolutionary Model Encompassing Substrate Specificity and Reactivity of Type I Polyketide Synthase Thioesterases

et al. 2014

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Bacterial polyketides are a rich source of chemical diversity and pharmaceutical agents. Understanding the biochemical basis for their biosynthesis and the evolutionary driving force leading to this diversity is essential to take advantage of the enzymes as biocatalysts and to access new chemical diversity for drug discovery. Biochemical characterization of the thioesterase (TE) responsible for 6-deoxyerythronolide macrocyclization shows that a small, evolutionarily accessible change to the substrate can increase the chemical diversity of products, including macrodiolide formation. We propose an evolutionary model in which TEs are by nature non-selective for the type of chemistry they catalyze, producing a range of metabolites. As one metabolite becomes essential for improving fitness in a particular environment, the TE evolves to enrich for that corresponding reactivity. This hypothesis is supported by our phylogenetic analysis, showing convergent evolution of macrodiolide-forming TEs.

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Section: Introductionmentioning

confidence: 99%

An Evolutionary Model Encompassing Substrate Specificity and Reactivity of Type I Polyketide Synthase Thioesterases

et al. 2014

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“…The nitrovinyl pathway development owes to the discovery of one-step conversion of nitroalkenes to hydroximoyl chlorides [ 147 ]. As depicted in Figure 8 for the synthesis of indole GSL, glucobrassicin, the conversion of nitroalkenes relies on the reaction of nitrovinyl derivatives with triethylsilane (i.e., hydride source) in the presence of a Lewis acid to provide substituted acetylhydroximol chlorides [ 10 ].…”

Section: Glucosinolates: Biosynthetic and Chemical Synthetic Pathwmentioning

confidence: 99%

Glucosinolates: Natural Occurrence, Biosynthesis, Accessibility, Isolation, Structures, and Biological Activities

et al. 2020

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Glucosinolates (GSLs) are secondary plant metabolites abundantly found in plant order Brassicales. GSLs are constituted by an S-β-d-glucopyrano unit anomerically connected to O-sulfated (Z)-thiohydroximate moiety. The side-chain of the O-sulfate thiohydroximate moiety, which is derived from a different amino acid, contributes to the diversity of natural GSL, with more than 130 structures identified and validated to this day. Both the structural diversity of GSL and their biological implication in plants have been biochemically studied. Although chemical syntheses of GSL have been devised to give access to these secondary metabolites, direct extraction from biomass remains the conventional method to isolate natural GSL. While intact GSLs are biologically inactive, various products, including isothiocyanates, nitriles, epithionitriles, and cyanides obtained through their hydrolysis of GSLs, exhibit many different biological activities, among which several therapeutic benefits have been suggested. This article reviews natural occurrence, accessibility via chemical, synthetic biochemical pathways of GSL, and the current methodology of extraction, purification, and characterization. Structural information, including the most recent classification of GSL, and their stability and storage conditions will also be discussed. The biological perspective will also be explored to demonstrate the importance of these prominent metabolites.

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“…The use of the conventional halogenation reactions can be avoided by reaction of conjugated nitroalkenes with titanium tetrachloride. 91 Dehydrohalogenation is most commonly achieved by addition of one equivalent of a tertiary amine base (usually triethylamine) to a solution or suspension of the hydroximic acid halide in an inert organic solvent such as diethyl ether (Scheme 15). A range of aliphatic, aromatic and heterocyclic nitrile oxides have been prepared by this method.…”

Section: Reactivitymentioning

confidence: 99%

Asymmetric 1,3-dipolar cycloadditions of acrylamides

2010

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This critical review, which is relevant to researchers in synthetic organic chemistry, focuses on asymmetric 1,3-dipolar cycloadditions with acrylamides. The use of chiral acrylamides as dipolarophiles leads to high levels of stereocontrol, due to conformational constraint in the acrylamides. Employment of chiral tertiary acrylamides containing nitrogen heterocycles is particularly effective in controlling the stereoselectivity. Following a general overview of 1,3-dipolar cycloadditions, the main body of the review focuses on asymmetric 1,3-dipolar cycloadditions of acrylamides with nitrile oxides, nitrones, diazoalkanes and azomethine ylides, with particular emphasis on the rationale for the observed stereocontrol (215 references)

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Synthesis of α-Functionalized and Nonfunctionalized Hydroximoyl Chlorides from Conjugated Nitroalkenes and Nitroalkanes

Cited by 48 publications

References 56 publications

An Evolutionary Model Encompassing Substrate Specificity and Reactivity of Type I Polyketide Synthase Thioesterases

An Evolutionary Model Encompassing Substrate Specificity and Reactivity of Type I Polyketide Synthase Thioesterases

Glucosinolates: Natural Occurrence, Biosynthesis, Accessibility, Isolation, Structures, and Biological Activities

Asymmetric 1,3-dipolar cycloadditions of acrylamides

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