An improved procedure for the preparation of the Dess-Martin periodinane

Ireland, Robert E.; Liu, Longbin

doi:10.1021/jo00062a040

Cited by 640 publications

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“…Organic solvents were dried before use by standard methods (38). Dess-Martin periodinane (39,40) was prepared according to literature procedures. m-Chloroperbenzoic acid was recrystallized from dichloromethane before use, and all other reagents were purchased from Sigma-Aldrich and used without further purification.…”

Section: Methodsmentioning

confidence: 99%

Potent Inhibitors of a Shikimate Pathway Enzyme from Mycobacterium tuberculosis

Reichau

Jiao

Walker

et al. 2011

Journal of Biological Chemistry

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Tuberculosis remains a serious global health threat, with the emergence of multidrug-resistant strains highlighting the urgent need for novel antituberculosis drugs. The enzyme 3-deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAH7PS) catalyzes the first step of the shikimate pathway for the biosynthesis of aromatic compounds. This pathway has been shown to be essential in Mycobacterium tuberculosis, the pathogen responsible for tuberculosis. DAH7PS catalyzes a condensation reaction between P-enolpyruvate and erythrose 4-phosphate to give 3-deoxy-D-arabino-heptulosonate 7-phosphate. The enzyme reaction mechanism is proposed to include a tetrahedral intermediate, which is formed by attack of an active site water on the central carbon of P-enolpyruvate during the course of the reaction. Molecular modeling of this intermediate into the active site reported in this study shows a configurational preference consistent with water attack from the re face of P-enolpyruvate. Based on this model, we designed and synthesized an inhibitor of DAH7PS that mimics this reaction intermediate. Both enantiomers of this intermediate mimic were potent inhibitors of M. tuberculosis DAH7PS, with inhibitory constants in the nanomolar range. The crystal structure of the DAH7PS-inhibitor complex was solved to 2.35 Å . Both the position of the inhibitor and the conformational changes of active site residues observed in this structure correspond closely to the predictions from the intermediate modeling. This structure also identifies a water molecule that is located in the appropriate position to attack the re face of P-enolpyruvate during the course of the reaction, allowing the catalytic mechanism for this enzyme to be clearly defined.Tuberculosis remains a serious global health threat with over a million deaths per year. The recent emergence of multidrugresistant strains of Mycobacterium tuberculosis, the pathogen that causes the lung disease, highlights the need for rapid development of new antibacterial drugs to combat tuberculosis (1-4).3-Deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAH7PS) 4 is an important enzyme in M. tuberculosis and other pathogens. It catalyzes the first committed step in the shikimate pathway, which is responsible for the biosynthesis of aromatic amino acids and other essential aromatic metabolites in microorganisms, plants, and apicomplexan parasites (5-7). This pathway is absent in humans, and inhibitors of amino acid biosynthesis have been shown to be effective antimicrobial and herbicidal agents (8, 9). Gene disruption studies have demonstrated that M. tuberculosis is not viable if the shikimate pathway is not operational (10). These findings make DAH7PS an attractive target for drug development.DAH7PS catalyzes the aldol-like condensation of P-enolpyruvate and D-erythrose 4-phosphate (E4P) to yield 3-deoxy-Darabino-heptulusonate 7-phosphate (Fig. 1a). The reaction mechanism has been subject to extensive study, and many of the key details of the mechanism have been elucidated (11-16). The reactio...

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Section: Methodsmentioning

confidence: 99%

Potent Inhibitors of a Shikimate Pathway Enzyme from Mycobacterium tuberculosis

Reichau

Jiao

Walker

et al. 2011

Journal of Biological Chemistry

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“…[21][22][23] Furthermore, results from certain of these iodane-mediated oxidations are compared to those obtained by anodic oxidation, a technique we are also evaluating as another environmentally benign means for the synthesis of orthoquinonoid cyclohexadienone synthons. …”

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confidence: 99%

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Quideau¹,

Pouységu²,

Deffieux³

et al. 2003

Arkivoc

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A series of 2-methoxy and 2-methylphenols have been submitted to oxygenative oxidation reactions using (1) the λ 3 -iodane DIB, (2) a non-explosive and non-moisture sensitive version of the λ 5 -iodane IBX, named SIBX for Stabilized IBX, and (3) anodic oxidation with the aim of identifying the best reaction conditions for preparing orthoquinonoid cyclohexadienone synthons. Both the use of DIB and anodic oxidation appeared equally valuable for making orthoquinone dimethyl ketals, but the λ 3 -and λ 5-iodane reagents are more appropriate to induce ortho-oxygenation of 2-methylphenols. In particular, SIBX emerged as a useful reagent for mediating ortho-hydroxylation into dimerizing orthoquinols, a tactic that can be applied to the synthesis of natural bis(monoterpenoids) such as aquaticol.

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“…The whole was extracted with ether, and the ethereal extracts were washed with saturated aqueous NaCl, dried, and concentrated to leave a pale yellow oil. Purification by flash chromatography [hexaneAcOEt (5 : 2)] gave 12b (280 mg, 82%) as a colorless oil, [ [42][43][44] (610 mg, 1.4 mmol) in CH 2 Cl 2 (10 ml). After having been stirred at room temperature for 45 min, the reaction mixture was poured into saturated aqueous NaHCO 3 (10 ml) containing Na 2 S 2 O 3 (1.8 g).…”

Section: E6s)-6-[[(11-dimethylethyl)dimethylsilyl]oxy]-4-hydroxy-6mentioning

confidence: 99%

“…The oxazole-olefin 13a desired for the intramolecular Diels-Alder reaction was then obtained in 89% yield by oxidation of 12a with the Dess-Martin periodinane. [42][43][44] When a 0.05 M solution of 13a in o-dichlorobenzene (o-DCB) was heated at 150°C for 48 h, the bicyclic pyridine 14a was obtained in 37% yield, together with recovered 13a (23%). On treatment of the solution at the higher temperature (180°C) for 24 h, both the yield of 14a and the recovery of 13a decreased to 19% and 10%, respectively.…”

mentioning

confidence: 99%

Use of the Oxazole-Olefin Diels-Alder Reaction in the Total Synthesis of the Monoterpene Alkaloids (-)-Plectrodorine and (+)-Oxerine

2006

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Oxazoles have been shown to behave as dependable azadiene components in Diels-Alder reactions.1) Since Kondrat'eva reported the first example of a Diels-Alder reaction of an oxazole with an olefin to produce a pyridine in 1957, 2,3) this methodology has become a valuable tool for the preparation of highly substituted pyridines, such as pyridoxine and its analogues. Despite an early recognition of the practical value of the oxazole-olefin Diels-Alder reaction, there are few reports applying this cycloaddition intramolecularly to the synthesis of pyridine-containing natural products. [4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] In the present study, we sought to explore the feasibility of intramolecular oxazole-olefin Diels-Alder reaction for an efficient construction of two monoterpene alkaloids possessing the cyclopenta[c]pyridine ring system. [20][21][22][23] Plectrodorine (1), selected as the first target for the monoterpene alkaloids, was isolated as a racemate together with isoplectrodorine (2) from the aerial parts of Plectronia odorata (Rubiaceae) by Koch and co-workers.24) The structure and relative stereochemistry of 1 were elucidated through a combination of spectral analysis and chemical transformation. The Koch group 25) then described the isolation of oxerine from the aerial parts of Oxera morieri (Verbenaceae) and proposed its absolute stereochemistry to be (5R,7S)-3 by partial synthesis of oxerine from harpagide of known absolute configuration. 26) We chose (5R,7S)-3 as the second target to demonstrate the versatility of our synthetic strategy, although racemic synthesis of oxerine has been accomplished by several research groups. [27][28][29][30] A brief account of the results reported here has been published in a preliminary form. 31)For the construction of the cyclopenta[c]pyridine skeleton via the intramolecular Diels-Alder reaction of oxazoles, we planned to employ the oxazole-olefin 4. The introduction of suitable olefinic dienophiles to the oxazole aldehyde 5 would provide 4, whereas the oxazole ring of 5 was envisaged to arise from the addition of a-lithiated methyl isocyanide to the g-butyrolactone 6 according to the procedure of Jacobi. 32,33) The requisite g-butyrolactone 6 was readily obtained from Seebach's dioxolanone 7. 34,35) Thus, reduction of 7 with BH 3 · Me 2 S followed by alkaline hydrolysis and acid-promoted lactone formation afforded 6 in 73% yield. The absolute configuration of 6 was further substantiated by the identity of specific rotation of the benzoate 8, derived from 6, with the data reported in the literature. 36) After protection of the tertiary hydroxy group in 6 with tert-butyldimethylsilyl triflate (TBDMSOTf) to afford the lactone 9, the formation of an oxazole ring was carried out by treatment of 9 with 2.5 eq of a-lithiated methyl isocyanide in THF at Ϫ78°C for 3 h followed by addition of AcOH, a slight modification of the Jacobi method, 32,33) giving the alcohol 10 in 66% yield. With a view to introducing an olefinic dienophile, the alcohol 10 was...

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An improved procedure for the preparation of the Dess-Martin periodinane

Abstract: dihydro-l,2-benziodoxol-3(lH)-one (3), has become the reagent of choice for the oxidation of primary and secondary alcohols to aldehydes and ketones, respectively.2

Cited by 640 publications

References 0 publications

Potent Inhibitors of a Shikimate Pathway Enzyme from Mycobacterium tuberculosis

Potent Inhibitors of a Shikimate Pathway Enzyme from Mycobacterium tuberculosis

Iodane-mediated and electrochemical oxidative transformations of 2-methoxy- and 2-methylphenols

Use of the Oxazole-Olefin Diels-Alder Reaction in the Total Synthesis of the Monoterpene Alkaloids (-)-Plectrodorine and (+)-Oxerine

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