Glycosylmanganese pentacarbonyl complexes: an organomanganese-based approach to the synthesis of C-glycosyl derivatives

DeShong, Philip; Soli, Eric D.; Slough, Greg A.; Sidler, Daniel R.; Elango, Varadaraj; Rybczynski, Philip J.; Vosejpka, Laura J. Smith; Lessen, Thomas A.; Le, Thuy X.; Anderson, G. B.; Philipsborn, W. Von; Vöhler, Markus; Rentsch, Daniel; Zerbe, Oliver

doi:10.1016/s0022-328x(99)00431-3

Cited by 17 publications

(16 citation statements)

References 37 publications

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“…The experimental results described herein, and in particular the observed stereoselectivities, do not immediately indicate any specific mechanism(s). Also, comparison with observations for addition of other metal fragments [3–5] does not clarify the picture much.…”

Section: Resultsmentioning

confidence: 84%

“…The few literature reports on the oxidative addition of glycosyl halides to metal complexes evidence that the control of stereochemistry is indeed a crucial issue: DeShong and co‐workers developed a strategy using glycosyl‐manganese pentacarbonyl complexes for highly stereoselective glycosyl functionalization [3] . However, they observed that the stereochemistry in the glycosyl‐manganese intermediate was dependent on the experimental conditions.…”

Section: Introductionmentioning

confidence: 99%

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Oxidative Addition of α‐Glycosyl Halides to a Platinum(0) Olefin Complex: Stereochemistry of Pt−C Bond Formation

et al. 2021

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The oxidative addition of α‐glucosyl and α‐galactosyl halides to the platinum(0) complex [Pt(2,9‐dimethyl‐1,10‐phenanthroline)(ethene)] has been investigated. In all cases the main reaction product is the five‐coordinate Pt(II) complex containing in axial position an α‐glycosyl fragment in the unusual 1C4 conformation. In the case of glucose, a minor product could be identified as the β isomer, which retains the typical 4C1 chair. The single crystal structures of two diastereomers are compared. The outcome of the reaction does not depend on the nature of the halide and is only slightly affected by the solvent. The addition mechanism is discussed, also in the light of literature data. Experimental data, along with DFT calculations, point towards a radical chain mechanism.

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Section: Resultsmentioning

confidence: 84%

Section: Introductionmentioning

confidence: 99%

Oxidative Addition of α‐Glycosyl Halides to a Platinum(0) Olefin Complex: Stereochemistry of Pt−C Bond Formation

et al. 2021

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“…Albrecht Salzer or Heinz Berke, or from the ETH, e.g. Luigi Venanzi and Paul Pregosin, but also from shared projects with the groups of Bönnemann at the Max Plank Institute in Mühlheim [2] and the DeShong group [3][4][5] in the US. His spectroscopic work started out with the analysis of natural products, and concerned many aspects of 15 N NMR.…”

Section: Main Research Interestsmentioning

confidence: 99%

“…[5] The reliability of the line shape fitting method was established by comparison of the data with results from solid-state 13 C or 31 P magic angle spinning NMR spectra that exhibited first-order splittings due to the scalar coupling with 55 Mn [22] and with the aid of test compounds like Li[AsF 6 ] or K 3 [Co(CN) 6 ] which allowed direct observation of the J-splitting of resonances in solution. [21] Branching into BioNMR Graduate students of the von Philipsborn group were recruited from many places.…”

Section: Measurement Of Coupling Constants To Quadrupolar Nucleimentioning

confidence: 99%

Synthesis and NMR Spectroscopic Characterization of Organometallics in the Laboratory of Wolfgang von Philipsborn: Reminiscences of Former Graduate Students

Hafner¹,

Nanz²,

Piantini³

et al. 2009

Chimia

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On the occasion of his 80 th birthday, former graduate students from the group of Prof. Wolfgang von Philipsborn from the Institute of Organic Chemistry, University of Zurich, describe from a personal perspective the scientific achievements of his group in the field of nuclear magnetic resonance, mainly applied to transition metals and in the field of organometallic chemistry. Interest in metal chemical shifts is driven by the need to understand reactivity of organometallic compounds in catalysis. Progress in the field is very much related to the technical development of NMR instruments. The range of experiments spans from simple 1D experiments with direct metal detection to 2D NMR experiments, in which metal frequencies are encoded via their attached protons or phosphorous ligands. Other examples come from the structural biology of metal-containing proteins or form the measurement of scalar couplings to quadrupolar nuclei via lineshape analysis. A particular emphasis is presented on how collaborations from various groups at the campus have been fruitful to the scientific progress in the von Philipsborn group. The article also contains a number of personal anecdotes that document life of the graduate students in his group at that time. C(sp 2 )) = 65-81 Hz 1 J ( 55 Mn, 13 C(sp 3 )) = 35-64 Hz d e e 1 J ( 55 Mn, 13 C(carbene)) = 97-131 Hz 1 J ( 55 Mn, 13 C(carbyne)) = 168-185 Hz 1 J ( 55 Mn, 31 P) = 191-226 Hz

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“…[1][2][3][4][5][6][7][8][9] Hence, methods for generating this type of heterocycle are very attractive. [10][11][12][13][14][15][16][17][18][19] Several sydnone derivatives are associated with a wide range of physiological activities including antimicrobial, anti-inflammatory, analgesic and antipyretic activities. [20][21][22] Consequently, chemists still enthusiastically pursue the syntheses of sydnone derivatives.…”

Section: Heterocyclic Analogues Of Chalcones Have Been Preparedmentioning

confidence: 99%

A Concise Synthetic Method for Sydnonyl-Substituted Pyrazoline Derivatives

Shih¹

2003

Synthesis

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The pyrazolines have been found to have diverse applications in medicine. They are known to be potent antibiotic or antioxidizing agents. Two types of sydnonyl-substituted a,bunsaturated ketones were synthesized by the Claisen-Schmidt condensation for the preparation of sydnonyl-substituted pyrazolines. One is the condensation of 3-(4-ethoxyphenyl)-4-formylsydnone (1) with acetone (2a) or acetophenone (2b), and the other is the condensation of 4-acetyl-3-arylsydnones 5 with various aryl aldehydes 6. Finally, 1H-pyrazoline derivatives 8 were synthesized successfully by reacting the appropriate a,b-unsaturated ketone precursors 7 with hydrazine hydrate.Heterocyclic analogues of chalcones have been prepared for biological studies. The a,b-unsaturated ketones can play as versatile precursors in the syntheses of the corresponding pyrazoline derivatives. 1-5 Moreover, the pyrazolines have been found to have diverse applications in medicine and agriculture. In particular, they are reported to be potent antibiotic and antioxidizing agents. 1-9 Hence, methods for generating this type of heterocycle are very attractive. 10-19 Several sydnone derivatives are associated with a wide range of physiological activities including antimicrobial, anti-inflammatory, analgesic and antipyretic activities. 20-22 Consequently, chemists still enthusiastically pursue the syntheses of sydnone derivatives. 23-28 Following reports of these activities, this study seeks to synthesize a series of pyrazolines that contain the sydnonyl moiety, with the aim of obtaining new biologically active compounds.The pyrazolines are usually prepared by the reactions of of a,b-unsaturated ketones and hydrazine hydrate. Although well known, this reaction has never been applied to the sydnone systems. Prompted by the biological activities of heterocyclic compounds and earlier interest in incorporating heterocyclic moieties in sydnones, [29][30][31][32][33][34][35] it was contemplated to synthesize some new sydnones that have pyrazolinyl moieties. In this present study, 4-[3-(4-ethoxyphenyl)sydnon-4-yl]but-3-en-2-one (3a) or 3-[3-(4-ethoxyphenyl)sydnon-4-yl]-1-phenylprop-2-en-1-one (3b) were prepared in high yields from the reaction of 3-(4-ethoxyphenyl)-4-formylsydnone (1) with acetone (2a) or acetophenone (2b) by the Claisen-Schmidt condensation 36,37 (Scheme 1). Treatment of compound 3a or 3b with hydrazine hydrate in 95% ethanol under various temperature conditions did not yield the desired cyclization product 4 (Scheme 1) though a crude solid was isolated. This condensation solid product was characterized as a hydrazone of compound 3 according to the IR and NMR analyses. This result implied that the electron-releasing property of 4-sydnonyl group may increase the electron density on the carbon-carbon double bond of a,b-unsaturated ketones and hinder the Michael addition of hydrazine to the a,bunsaturated ketones 3. Scheme 1 1: Ar = p-C 2 H 5 OC 6 H 4 ; 2a: R¢ = CH 3 ; 2b: R¢ = C 6 H 5To solve this problem, another type of sydnonyl-substituted a,b-unsaturat...

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Glycosylmanganese pentacarbonyl complexes: an organomanganese-based approach to the synthesis of C-glycosyl derivatives

Cited by 17 publications

References 37 publications

Oxidative Addition of α‐Glycosyl Halides to a Platinum(0) Olefin Complex: Stereochemistry of Pt−C Bond Formation

Oxidative Addition of α‐Glycosyl Halides to a Platinum(0) Olefin Complex: Stereochemistry of Pt−C Bond Formation

Synthesis and NMR Spectroscopic Characterization of Organometallics in the Laboratory of Wolfgang von Philipsborn: Reminiscences of Former Graduate Students

A Concise Synthetic Method for Sydnonyl-Substituted Pyrazoline Derivatives

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