Oxidation of Alcohols by Activated Dimethyl Sulfoxide and Related Reactions: An Update

Tidwell, Thomas T.

doi:10.1055/s-1990-27036

Cited by 427 publications

(161 citation statements)

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“…Contrary to (3R)-llc, the 2-(N-benzy1amino)-3-(chloromethy1)valeronitrile 28 underwent Swern oxidation (42) into the imine 29 with only 30% yield; use of an excess of DMSO and (COC1)2 reagents did not improve the yield but entailed mainly formation of methylthiomethylamine derivative (3S)-30 (18,19,44). Use of N,N-diisopropylethylamine, known to limit, by steric hindrance, formation of methylthiomethyl ether (44) in the Swern oxidation of alcohol, totally inhibited the reaction of (3s)-28.…”

Section: Methodsmentioning

confidence: 99%

“…of imidazole, cat. DMAP) (19,20) followed by deacetylation with potassium carbonate in methanol provided the (2s)-2-(tert-butyldimethylsiloxymethyl)-butanol 25 in 84% overall yield. Swern oxidation (DMSO, (COCI),, Et-iPr2N) (18)" gave the corresponding aldehyde (2R)-26, which was directly treated with an excess of TMSCN in the presence of zinc iodide in diethyl ether at 0°C.…”

Section: Methodsmentioning

confidence: 99%

“…Swern oxidation is currently used to prepare carbonyl compounds from primary or secondary alcohols (1 8), but only a few reports concern the oxidation of amines into imines by the DMSO((COCl),/NEt, reagent (42); effectively, treatment of the N-benzylamine l l c under Swern oxidation conditions (18,43) led to the expected imine, i.e., the (3R)-2-(phenylmethyleneamino)-4-chloro-3-methylbutyronitrile 3, in 70% yield, as well as 5% of methylthiomethylamine 12 as by-product (44) (Scheme 4).…”

Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

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Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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(3R)-2-(N-Benzylideneamino)-4-chloro-3-methylbutyronitrile 3, prepared from the commercially available methyl (2S)-3-hydroxy-2-methyl propionate 5 (96% ee), readily underwent potassium carbonate induced cyclization to provide, after acid hydrolysis (6 N HCl) and chromatography, the (1S,2S)-norcoronamic acid 1a with 88% diastereoselectivity and > 95% enantiomeric excess. From (2R)-2-(hydroxymethyl)butyl acetate 23 (> 88% ee) obtained by enzymatic enantioselective hydrolysis with lipase PS, was prepared the (3S)-2-(N-benzylideneamino)-3-(chloromethyl)valeronitrile 29, which after base-induced cyclization (K2CO3) and acid (6 N HCl) or basic (0.8 N NaOH) hydrolysis led to the non-natural (1R,2R)-coronamic acid 18 (> 88% ee). Also from this same acetate (2R)-23 was prepared the (3R)-3-(chloromethyl)-2-[(diphenylmethylene)amino]pentanenitrile 37, which provided the (1S,2S)-coronamic acid 17 (> 88% ee) after base-induced cyclization (K2CO3 or LDA) and acid hydrolysis (6 N HCl). It is noteworthy that these short synthetic sequences, which do not require any expensive chiral auxiliary or optically active precursors, do not alter the enantiomeric purity of the stereogenic centers of these 2,3-methanoamino acids. However, the E diastereoselectivity of these cyclizations was not improved by using bulky N-(diphenylmethylene)amino substituent, contrary to results of some molecular mechanic calculations (MAD).

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Omcrique a Partir De L'acttate De 2-(hydroxymcthyl)butyle (mentioning

confidence: 99%

See 1 more Smart Citation

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Gaucher¹,

Ollivier²,

Marguerite³

et al. 1994

Can. J. Chem.

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“…For example, alkoxysulfonium ions, which are key intermediates of the Swern Moffatt type oxidation, 48,49 and Kornblum oxidation, 50,51 can be used as intermediates in the integration of electrochemical oxidation and chemical oxidation. 52 Carbocations, such as diarylcarbenium ions 31,32 generated by oxidative C H bond dissociation using the cation pool method react with dimethyl sulfoxide (DMSO) to give alkoxysulfonium ion pools, which have been well characterized by NMR.…”

Section: Integrated Electrochemical Chemical Oxidation Viamentioning

confidence: 99%

Recent Developments in the ^|^ldquo;Cation Pool^|^rdquo; Method

Yoshida

Ashikari

Matsumoto

et al. 2013

J. Synth. Org. Chem. Jpn.

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“…Main reaction pathway (the central column in Figure 1): DMSO (1) and TFAA (2) in DCM react at low temperatures to form intermediate 1 (3). This compound can form a white precipitate [26] and is only stable below −30°C [29]. In the absence of the Pummerer rearrangement occurring, intermediate 1 (3) reacts as desired with 1-phenylethanol (4) to form intermediate 2 (5), with the free electron pair on the hydroxyl group of (4) attacking the positive charge on the sulfur on (3).…”

Section: Introductionmentioning

confidence: 99%

Moffat-Swern Oxidation of Alcohols: Translating a Batch Reaction to a Continuous-Flow Reaction

Bleie¹,

Roberto²,

Dearing³

et al. 2015

J Flow Chem

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The Moffatt-Swern oxidation (MSO) is a multistep, versatile, metal-free reaction by which alcohols are transformed into aldehydes and ketones. Batch MSO requires low temperatures (−70°C) due to a highly exothermic reaction step that generates intermediates. This work shows that a rigorous investigation of the MSO in batch can be used as a stepping-stone to its implementation in a continuous-flow reactor (CFR). This work has two parts: the first part details the investigation of MSO in batch; the second covers the translation of the knowledge derived from batch to a CFR. The MSO batch reaction was performed under cryogenic conditions with real-time process monitoring. The reaction was monitored with Raman spectroscopy and could be tracked throughout the reaction. All concentrations were validated using offline high-performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GC-MS). Two configurations of the CFR were produced. Configuration 1 used the traditional batch methodology in terms of reagent addition and reaction conditions. Configuration 2 used the information derived from the batch reaction, changing the order of the reagent addition and increasing the temperature of the reactor. Real-time quantitative monitoring of chemical yield in the CFR was demonstrated via Raman spectroscopy and partial least squares (PLS) regression modeling. Reaction yield was accurately predicted every 15 s, reducing the need for chromatographic validation once the model was built. Configuration 2 was shown to perform comparably to configuration 1 at low temperature and far outperforming it at higher temperatures. Both CFR configurations performed significantly better than the batch setup in terms of temperature and yield, as was expected.

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Oxidation of Alcohols by Activated Dimethyl Sulfoxide and Related Reactions: An Update

Cited by 427 publications

References 0 publications

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Total asymmetric syntheses of (1S,2S)-norcoronamic acid, and of (1R,2R)- and (1S,2S)-coronamic acids from the diastereoselective cyclization of 2-(N-benzylideneamino)-4-chlorobutyronitriles

Recent Developments in the ^|^ldquo;Cation Pool^|^rdquo; Method

Moffat-Swern Oxidation of Alcohols: Translating a Batch Reaction to a Continuous-Flow Reaction

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