Inactivation of S-adenosylhomocysteine hydrolase with haloethyl and dihalocyclopropyl esters derived from homoadenosine-6′-carboxylic acid

Guillerm, Georges; Muzard, Murielle; Glapski, Cédric

doi:10.1016/j.bmcl.2004.09.050

Cited by 9 publications

(2 citation statements)

References 29 publications

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“…We were pleased to find that both n -propoxide and isopropoxide underwent efficient addition, providing the corresponding cyclopropyl ethers 20ab and 20ac as sole products in high yields and excellent diastereoselectivities (Table , entries 1 and 2). Benzyl-protected cyclopropanol 20ad was also obtained in good yield in the reaction carried out in the presence of benzylic alcohol (entry 3). O -Nucleophiles bearing additional functional groups were also successfully employed in this transformation.…”

Section: Resultsmentioning

confidence: 99%

Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles

et al. 2011

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A diastereoconvergent formal nucleophilic substitution of bromocyclopropanes with oxygen- and sulfur-based nucleophiles is described. The reaction proceeds via in situ formation of a highly reactive cyclopropene intermediate and subsequent diastereoselective addition of a nucleophile across the strained C═C bond. Three alternative means of controlling the diastereoselectivity of addition have been demonstrated: (1) thermodynamically driven epimerization of enolizable carboxamides, (2) steric control by bulky substituents, and (3) directing effect of carboxamide or carboxylate functions.

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Section: Resultsmentioning

confidence: 99%

Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles

et al. 2011

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“…Reaction of 1a with allyl alcohol was accompanied with a base-assisted migration of the double bond providing potentially deprotectable vinyloxycyclopropane 3ae as the only product (entry 6). Benzyl-protected cyclopropanol 3af was also obtained in good yield (entry 7). Addition of a nitrogen-based nucleophile, N -methylacetamide, also proceeded smoothly producing cyclopropylamine derivative 3ag (entry 8).…”

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confidence: 99%

Highly Diastereoselective Formal Nucleophilic Substitution of Bromocyclopropanes

et al. 2009

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A highly diastereoselective formal nucleophilic substitution of bromocyclopropanes with oxygen- and nitrogen-based nucleophiles was demonstrated. The reaction proceeds via a base-assisted dehydrohalogenation producing a cyclopropene intermediate, which subsequently undergoes addition of a pronucleophile across the strained double bond. Very high chemoselectivity toward addition of primary and secondary alkoxides, as well as N-nucleophiles, in the presence of tert-butoxide base was observed, whereas phenoxides did not undergo addition under these reaction conditions. Facial selectivity of the addition can be efficiently controlled either by sterics or through a directing effect of an amide, carboxylate, and an o-aminomethylphenol function. Employment of tethered optically active amino alcohols as pronucleophiles allowed for efficient assembly of homochiral bicyclic compounds.

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Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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Inactivation of S-adenosylhomocysteine hydrolase with haloethyl and dihalocyclopropyl esters derived from homoadenosine-6′-carboxylic acid

Cited by 9 publications

References 29 publications

Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles

Diastereoselectivity Control in Formal Nucleophilic Substitution of Bromocyclopropanes with Oxygen- and Sulfur-Based Nucleophiles

Highly Diastereoselective Formal Nucleophilic Substitution of Bromocyclopropanes

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

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