Expedient synthesis of natural (S)-sinefungin and of its C-6′ epimer

Barton, D. H. R.; Géro, S. D.; Quiclet‐Sire, Béatrice; Samadi, M.

doi:10.1039/p19910000981

Cited by 46 publications

(50 citation statements)

References 18 publications

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“…The relative and absolute stereochemistries were confirmed by the X-ray crystallographic analysis ( Figure 4). [16] Reductive removal of xanthate 10 using nBu 3 SnH and AIBN under Barton-McCombie conditions [17] was carried out at 80°C to provide alkane 11 in good yield (78 %). We then examined the conversion of NO 2 into H using the same reagents, [18] but this Scheme 4.…”

Section: Resultsmentioning

confidence: 99%

Total Synthesis of Estradiol Methyl Ether and Its Five‐Pot Synthesis with an Organocatalyst

2018

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Enantioselective total synthesis of estradiol methyl ether has been accomplished in a highly diastereo‐ and enantioselective manner. The key reaction is diphenylprolinol silyl ether mediated domino Michael/aldol reaction to afford bicyclo[4.3.0]nonane derivatives with A, C, and D rings of the steroids as a single isomer with excellent enantioselectivity. Each reaction was optimized, and the total synthesis could be accomplished in 12 pots with 10 purifications using silica gel, resulting in an overall yield of 6.8 %. The reaction sequence and reaction conditions were then optimized in terms of pot economy, whereupon estradiol methyl ether could be synthesized using five reaction vessels with four purifications in an overall yield of 15 %. Notably, six reactions, namely, oxidation, hydrogenation, formation of acid chloride, Friedel–Crafts reaction, deprotection, and reduction could be carried out in the last one‐pot sequence.

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Section: Resultsmentioning

confidence: 99%

Total Synthesis of Estradiol Methyl Ether and Its Five‐Pot Synthesis with an Organocatalyst

2018

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“…Thus, compounds 15 [5,9] and 6 were combined under our usual radical conditions to produce 16 (two stereoisomers at C-7) in 18% yield. Amide derivatives 16a and 16b were separated by HPLC and submitted separately to Hofmann degradation with [bis(trifluoroacetoxy)iodo]benzene.…”

Section: Resultsmentioning

confidence: 99%

“…The organic layer was washed with saturated NaHCO 3 (30 mL), brine (30 mL) and dried. Evaporation of the solvent gave a residue which was purified by silica gel column chromatography (heptane/ethyl acetate -7-carboxamido-5,6,7,8,9,10hexadeoxy-2,3-O-(isopropylidene)-10-methoxycarbonyl-]-β-D-decaribofuranose (16): A solution of 5-iodoribose 6 (2 g; 6.36 mmol) in THF/H 2 O (8/2) (10 mL) under a nitrogen atmosphere was treated (in 5 portions) with a solid mixture composed of CuI (1.46 g; 9.6 mmol) and Zn powder (2 g; 32 mmol) followed by a solution of acrylate 15 [5,9] (4.49 g; 19.1 mmol) in THF (10 mL). The reaction mixture was stirred with a vibromixer until disappearance of the starting material, diluted with ether, the suspension filtered through Celite and the resulting solution washed with brine.…”

Section: Methodsmentioning

confidence: 99%

A Radical-Based Strategy for the Synthesis of Higher Homologues of Sinefungin

Maria

Silva

Fourrey³

2000

Eur. J. Org. Chem.

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“…The compound was isolated from Streptomyces griseolus [127], and has been synthesized via several chemical routes [128][129][130][131][132][133][134]. Sinefungin (39) and even more its close analogue dehydrosinefungin (40, A9145C; Figure 9.1) are highly potent competitive inhibitors of MTases [135][136][137][138], CFA synthase [139] and ACC synthase [140], with the observed inhibition constants often being much lower than those with AdoHcy (2).…”

Section: Sinefunginmentioning

confidence: 99%

S‐Adenosyl‐L‐Methionine and Related Compounds

Dalhoff¹,

Weinhold

2008

Modified Nucleosides

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The sulfonium compound S-adenosyl-L-methionine (AdoMet, also known as SAM or SAMe, 1) is one of the most versatile biomolecules in nature and one of the most widely used enzyme substrates, second perhaps only to adenosine triphosphate (ATP) (Schemes 9.1 and 9.2). AdoMet (1) may be found in all phyla of life, and is one of the molecules crucial for the existence of living organisms. First identified by Cantoni in 1953 [1, 2] as the active methyl donor formed from L-methionine and ATP, AdoMet (1) proved to be not only the major methyl donor in nature but also to be involved in many other metabolic reactions [3,4]. The versatility of the cofactor is based on the reactivity of the pivotal sulfonium center, which activates the adjacent carbon atoms for nucleophilic attack, deprotonation, and radical formation. This leads to a unique cofactor in which all constituents are used in biochemical reactions. The group transfer reactions result in the release of one of three different thioether products which are more stable than the sulfonium compound, and thereby providing the driving force for these enzyme-catalyzed reactions. These highly preferable thermodynamics of AdoMet-dependent transfer reactions result in a strong preference for this cofactor compared, for example, to other methyl donors such as N5-methyltetrahydrofolate. Due to the electron lone pair in addition to the three different substituents, the sulfonium group is chiral, and the naturally occurring AdoMet (1) is S-configured at sulfur [5].Many other naturally occurring alkylated thioadenosines are derived from AdoMet (1) such as S-adenosyl-L-homocysteine (AdoHcy, also called SAH, 2) and 5 0 -deoxy-5 0 -methylthioadenosine (MTA, 3) (Scheme 9.3), although these compounds and their related 5 0 -thioethers are beyond the scope of this chapter. AdoMet (1) and its derivatives are involved in key metabolic reactions, cell cycle regulation and the storage of epigenetic information, which makes them not only highly interesting for studying biological pathways but also as in-vitro or in-vivo biochemical tools and candidates for diagnostics and therapeutics.

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Expedient synthesis of natural (S)-sinefungin and of its C-6′ epimer

Cited by 46 publications

References 18 publications

Total Synthesis of Estradiol Methyl Ether and Its Five‐Pot Synthesis with an Organocatalyst

Total Synthesis of Estradiol Methyl Ether and Its Five‐Pot Synthesis with an Organocatalyst

A Radical-Based Strategy for the Synthesis of Higher Homologues of Sinefungin

S‐Adenosyl‐L‐Methionine and Related Compounds

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