Synthesis of an optically active carbocyclic derivative of (+)-hydantocidin

Sano, Hiromi; Sugai, Soji

doi:10.1016/0957-4166(95)00140-k

Cited by 27 publications

(15 citation statements)

References 34 publications

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“…The reaction gave the title compound 3 as a yellow solid (12 mg, 95 %) (mp 150 o C, lit. 18,29 158-160 o C) with spectral data identical to those reported in the literature. 18,29 NMR spectra of compounds 3, 9-11, 13-20, 22, 24, 26, 27, (1R)-28b, (1S)-28b, 29c,d, 31c, 33c, 36-38…”

Section: Methodssupporting

confidence: 74%

“…5 Herbicidal activity, however, was maintained when the oxygen in the furan ring was replaced with a carbon to form the carbocyclic analogue (3). 18 Many of the synthetic strategies for the synthesis of hydantocidin and its analogues 10,12,15,19,20 have revolved around the use of sugar derivatives to generate the desired stereochemistry of the hydroxyl groups in the furan ring. Using this strategy, hexofuranose, [21][22][23][24] hexopyranose [25][26][27] and tetrofuranose 28 analogues have been generated.…”

Section: Hnmentioning

confidence: 99%

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Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

et al. 2005

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The phosphine-catalyzed [3 + 2]-cycloaddition of 5-methylenehydantoins 4 with the ylides 5, derived from addition of tributylphosphine to the 2-butynoic acid derivatives, 6a-d, gives spiro-heterocyclic products. The camphor sultam derivative 6b gives optically active products. Noteable was that the ylides derived from ethyl 2-butynoate and the 3-(2-butynoyl)-1,3-oxazolidin-2-one derivatives 6c and 6d gave spiro-heterocyclic products with reverse regioselectivities. The N,N-dibenzylprotected cycloadduct has been converted to carbocyclic hydantocidin and 6,7-diepi-carbocyclic hydantocidin.

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Section: Methodssupporting

confidence: 74%

Section: Hnmentioning

confidence: 99%

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

et al. 2005

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“…Later in 1995, Sano et al reported the synthesis of the carba-analogue of hydantocidin 95 , in which the oxygen atom of the d -ribose unit has been replaced by a methylene unit. After finding that the racemic carba-hydantocidin maintained the herbicidal activity [ 61 ], they focused on the synthesis of the optically active compound, which was prepared from easily available d -gulono-l,4-lactone [ 62 ]. Oxidative cleavage of gulonolactone 104 with sodium periodate, followed by formation of an intermediate isopropyl acetal and reaction with dimethyl methylphosphonate and n -butyl lithium, afforded cyclopentenone 105 ( Scheme 20 ).…”

Section: Synthesis Of Hydantoinsmentioning

confidence: 99%

Synthesis of Spironucleosides: Past and Future Perspectives

2017

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Spironucleosides are a type of conformationally restricted nucleoside analogs in which the anomeric carbon belongs simultaneously to the sugar moiety and to the base unit. This locks the nucleic base in a specific orientation around the N-glycosidic bond, imposing restrictions on the flexibility of the sugar moiety. Anomeric spiro-functionalized nucleosides have gained considerable importance with the discovery of hydantocidin, a natural spironucleoside isolated from fermentation broths of Streptomyces hygroscopicus which exhibits potent herbicidal activity. The biological activity of hydantocidin has prompted considerable synthetic interest in this nucleoside and also in a variety of analogues, since important pharmaceutical leads can be found among modified nucleoside analogues. We present here an overview of the most important advances in the synthesis of spironucleosides.

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“…The synthesis of (+)-carbocyclic analogue 112 of the spirohydantoin nucleoside (Scheme 23) starts from optically active ketone 109, which is derived from Dgulono-1,4-lactone. 33,34 Heating 109 with potassium cyanide and ammonium chloride in methanol-water at 90 °C provides the α-aminonitrile 110a [(1S,2S,3R,4R)-isomer] in 33% yield in a mixture with its 1-epimer (11%).…”

Section: 3-diazaspiro[44]nonanementioning

confidence: 99%

“…Treatment of 110a with chlorosulfonyl isocyanate, followed by hydrolysis with hydrochloric acid, affords spirohydantoin 111 in 64% yield (Scheme 23). 33,34 Hydrogenolysis of the benzyl ether function with hydrogen over 10% palladium-on-carbon affords the optically active 112 in 98% yield. The replacement of the oxygen atom with a carbon atom in the D-ribofuranose ring of the natural compound retains herbicidal activity.…”

Section: 3-diazaspiro[44]nonanementioning

confidence: 99%

Stereoselective Reactions in Preparation of Chiral α-Heteraspiro[m.n]alkanes

Undheim

2015

Synthesis

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The biological importance and wide occurrence of spirane systems in nature have stimulated studies in spirane chemistry. The fundamental spirane framework consists of two monocyclic rings linked in an orthogonal relationship by a common ring carbon. This review covers families of annular α-monoheteraspiranes starting with α-heteraspiro[2.4]heptanes and terminating with α-hetera[5.6]dodecanes; the annular heteroatoms are N, O, or S. The spirane systems are arranged according to the relative size of the two monocyclic rings with highest priority for the smaller ring, Often optically active spiranes are prepared for biological reasons by chemical modifications of natural products related to the spirane to be prepared. Chiral auxiliaries are useful in the introduction and control of stereochemistry in the construction of spiranes as intermediates in the preparation of novel amino acids and nucleosides. Another aspect of chiral spirane chemistry concerns modifications and conformational restrictions introduced in natural carbohydrates, nucleosides, and amino acids. 1 Introduction 2 Heteraspira[2.m]alkanes 3 Heteraspira[3.m]alkanes 4 Heteraspira[4.m]alkanes 5 Heteraspira[5.m]alkanes Key words α-heteraspiranes, chirons, stereoselective syntheses, spiroannulations, spirocyclic amino acids, spirocyclic nucleosides 2 Heteraspiro[2.m]alkanes 2.1 Heteraspiro[2.4]heptanes 2.1.1 4,6-Diazaspiro[2.4]heptane The Seebach chiron, tert-butyl (2S)-2-tert-butyl-3methyl-4-oxoimidazoline-1-carboxylate, was developed for the stereoselective construction of α-amino acids. 11 The chiron has also been used for the stereoselective synthesis of cyclic amino acids via a spirane. During lithiation of tertbutyl (2S)-2-tert-butyl-3-methyl-4-oxoimidazoline-1-carboxylate at the 5-position, the tert-butyl substituent effectively shields one face of the ylide from electrophilic attack. Thus acetate 1 (Scheme 1) is available from lithiated Seebach chiron and methyl α-bromoacetate. In a synthesis of 1-amino-2,2-dideuteriocyclopropane-1-carboxylic acid (4) via spirane 3, substrate 1 is stepwise lithiated by lithium

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Synthesis of an optically active carbocyclic derivative of (+)-hydantocidin

Cited by 27 publications

References 34 publications

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

Synthesis of Spironucleosides: Past and Future Perspectives

Stereoselective Reactions in Preparation of Chiral α-Heteraspiro[m.n]alkanes

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Synthesis of an optically active carbocyclic derivative of (+)-hydantocidin

Cited by 27 publications

References 34 publications

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

Synthesis of Carbocyclic Hydantocidins via Regioselective and Diastereoselective Phosphine-Catalyzed [3 + 2]-Cycloadditions to 5-Methylenehydantoins

Synthesis of Spironucleosides: Past and Future Perspectives

Stereoselective Reactions in Preparation of Chiral α-Hetera­spiro[m.n]alkanes

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Stereoselective Reactions in Preparation of Chiral α-Heteraspiro[m.n]alkanes