Total synthesis of (+)-castanospermine from D-mannose

Setoi, Hiroyuki; Takeno, Hidekazu; Hashimoto, Masashi

doi:10.1016/s0040-4039(00)98767-7

Cited by 54 publications

(11 citation statements)

References 12 publications

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“…Starting from commercial 2,3:5,6-di-O-isopropylidene-D-mannose (3), reduction with LAH as described, 11 provided diol 4 (Scheme 3) that after routine transformations involving selective O-protection as the monosilyl (5a) 12 and monobenzoate (5b) 13 derivatives, followed by oxidation of the remaining secondary alcohol, addition of cyanide, and subsequent mesylation gave compounds 6a and 6b, respectively, as a mixture of diastereoisomers at C4, which we did not try to separate, but were submitted together to further reaction. Formation of the alkylidenecarbene species as usual 6 gave the cyclopentane derivatives 7a (7%) and 8a (18%), isolated in a 25% total yield (Scheme 3).…”

Section: Resultsmentioning

confidence: 99%

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The synthesis of polyoxygenated, enantiomerically pure cyclopentane derivatives on route to neplanocin A stereoisomers via alkylidenecarbene species prepared from sugar templates

Nhien¹,

Soriano²,

Marco‐Contelles³

et al. 2009

Carbohydrate Research

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Section: Resultsmentioning

confidence: 99%

“…Bases and solvents were used as supplied. 13 C NMR resonances have been assigned by using standard NMR (DEPT, COSY, HSQC) experiments. FTIR spectra were obtained neat using ATR and are reported in cm À1 .…”

Section: Methodsmentioning

confidence: 99%

The synthesis of polyoxygenated, enantiomerically pure cyclopentane derivatives on route to neplanocin A stereoisomers via alkylidenecarbene species prepared from sugar templates

Nhien¹,

Soriano²,

Marco‐Contelles³

et al. 2009

Carbohydrate Research

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“…Setoi et al [12][13][14] have obtained DNJ (1) by treatment of 13 a protected form of DNJ (1) with aqueous TFA for 12 h, which has been prepared from D-mannose in 14 steps and 0.4% overall yield.…”

Section: Resultsmentioning

confidence: 99%

“…Behling et al 11 described a synthesis of DNJ (1) from L-sorbose that requires the isolation of only two intermediates and the use of only one protection/deprotection protocol. Setoi et al [12][13][14] described a synthesis of DNJ (1) from D-mannose by a multi-step approach with protecting/deprotecting group manipulation. To date several syntheses of DNJ (1) and analogues have been described.…”

Section: Introductionmentioning

confidence: 99%

A formal total synthesis of deoxynojirimycin from D-glucitol

Braga

Kato

2003

J. Braz. Chem. Soc.

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Descrevemos a síntese formal da desoxinojirimicina usando D-glucitol como material de partida economicamente atraente. Através de uma seqüência de reações de proteção e desproteção seletivas e reações de substituição nucleofílica obtivemos diversos intermediários isopropilidênicos. A formação de um epóxido intermediário e sua subseqüente abertura, através de uma reação nucleofílica intramolecular, levou à obtenção do heterociclo 1,5-didesoxi-1,5-diamino-2,3-O-isopropilideno-6silila-D-glucitol, que é um precursor da desoxinojirimicina (DNJ). This report deals with the formal synthesis of deoxynojirimycin using D-glucitol as an inexpensive starting material. Through a sequence of several selective protection/deprotection and nucleophilic substitution reactions, many isopropylidene derivatives were obtained. Formation of an epoxide intermediate and its subsequent ring opening, via intramolecular nucleophilic substitution, leads to the synthesis of heterocyclic 1,5-dideoxy-1,5-diamine-2,3-O-isopropylidene-6-silyl-D-glucitol, which is a precursor of deoxynojirimycin (DNJ).

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“…Nothing is known at present concerning the inhibitory action on intestinal aglucosidases. The l-epimer of castanospermine (231) was synthesized in the course of various castanospermine syntheses (BERNOTAS and GANEM 1984;SETOI et al 1985;INA and KIBAYASHI 1993). In a comparison of the inhibition of sucrase by various castanospermine derivatives, 231 falls between castanospermine (222) and the weak inhibitor I-deoxycastanospermine (238) on the activity scale (HENDRY et al 1987(HENDRY et al , 1988WINCHESTER et al 1990;ROBINSON et al 1992) (Table 14).…”

Section: Castanospermine Derivatives A) Epimers Deoxy Derivatives Amentioning

confidence: 99%

Chemistry and Structure-Activity Relationships of Glucosidase Inhibitors

Junge¹,

Matzke²,

Stoltefuß³

1996

Oral Antidiabetics

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A. IntroductionWhen intestinal sucrase and pancreatic a-amylase were identified at Bayer as new targets for improved diabetes therapy (PULS et al. 1973), the problem remained of the best way to find a potent and selective inhibitor of these enzymes. The medicinal chemist today has two alternatives in the search for a first lead compound, firstly the screening of thousands of compounds with maximum structural diversity in a random screening approach, or secondly the rational design of a lead compound, when the biochemical mechanism and the structure of the enzyme are weIl known. In the late 1960s, when we started to look for such potent and selective inhibitors, we had to choose the random screening approach, relying mainly on testing of extracts of the culture broths of microorganisms.Today the mechanism of enzymatic splitting of sucrose by intestinal sucrase is fairly weIl understood. First the glucosidic oxygen atom of sucrose is protonated via a carboxyl group of the enzyme. The splitting of the glucosidic C-O bond is further facilitated by the glucosyl cation being stabilized by a second carboxylate group of the enzyme (COGOLI and SEMENZA 1975). FinaIly, the glucosyl cation reacts with water to give the products 0-glucose and o-fructose. The protonated sucrose molecule land the glucosyl cation 11 are two high-energy intermediates of the enzymatic reaction. Today we know that mimics of such high-energy intermediates are often potent inhibitors of the enzyme. Accordingly, compounds similar in structure to o-glucose but with an easily protonated basic N-atom either in the position of the anomeric oxygen atom (inhibitor type I) or in the position of the ring oxygen atom (inhibitor type 11) should be potent inhibitors of sucrase (Fig. 1). Interestingly, both types of inhibitors represented by either acarbose or I-deoxynojirimycin were found in our random screening. In the foIlowing sections these two types of inhibitors are not discussed in a historical order but under structural criteria. Not included in this discussion are the a-amylase inhibitors of protein nature because there is no evidence that they will find any therapeutic application.

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Total synthesis of (+)-castanospermine from D-mannose

Cited by 54 publications

References 12 publications

The synthesis of polyoxygenated, enantiomerically pure cyclopentane derivatives on route to neplanocin A stereoisomers via alkylidenecarbene species prepared from sugar templates

The synthesis of polyoxygenated, enantiomerically pure cyclopentane derivatives on route to neplanocin A stereoisomers via alkylidenecarbene species prepared from sugar templates

A formal total synthesis of deoxynojirimycin from D-glucitol

Chemistry and Structure-Activity Relationships of Glucosidase Inhibitors

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