A New Role for Sulfenate Anions: Organocatalysis

Schwan, Adrian L.

doi:10.1002/cctc.201402817

Cited by 15 publications

(5 citation statements)

References 12 publications

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“…The transition‐metal‐free synthesis of trans ‐stilbenes was also realized by photoinduced direct C−H arylation of alkenes at room temperature . Sulfenate anions and their conjugate acids, sulfenic acids, are highly reactive intermediates in biochemistry and organic synthesis, but no examples of sulfenate anion catalysts are previously know.…”

Section: Methodsmentioning

confidence: 99%

Density Functional Determination of the Energetics of the Formation of trans‐Stilbene Catalyzed by Sulfenate Anions

et al. 2016

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trans-Stilbenei sa ni mportantb uilding block of useful materials such as dyes, fluorescent whiteners, liquid crystals, pigments,o ptical brighteners, scintillators,a nd organic light-emitting diodes. Taking cue from an innovative study devoted to the synthesis of these systems, we explored, throughad ensity functional theory investigation,t he mechanism of the conversion of benzylc hloride into trans-stilbene catalyzed by sulfenate anions;w ee xamined all steps of the reaction to rationalize the experimental findings throughd etermination of both the thermodynamic and kinetic features.

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Section: Methodsmentioning

confidence: 99%

Density Functional Determination of the Energetics of the Formation of trans‐Stilbene Catalyzed by Sulfenate Anions

et al. 2016

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“…Following procedure C, compound 8 (0.50 g, 1.55 mmol) as the substrate gave product 10 (0.55 g, 98%) as a white solid: mp 97. 2,4-Dimethoxy-6-phenethylbenzaldehyde (12). Pd/C (0.3 g, 10% by wt) was added to a solution of 6 (3.0 g, 11.18 mmol) in EtOAc (60 mL).…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…In view of the biological potential of cajaninstilbene acid (1) and amorfrutins A (2) and B (3), several synthetic routes for these compounds have been developed. These are focused on manipulation of the double bond in the stilbene unit parent, and various protocols have been developed, including use of the (1) Wittig reaction, 11 (2) benzylic metalation followed by alkylation, 12 and (3) Sonogashira coupling to link an aryltriflate with a phenylacetylene. 13 In a recent report of the synthesis of cajaninstilbene acid (1) and amorfrutin A (2) and their analogues, Julia olefination and monobenzylation followed by desulfonylation with SmI 2 were used as key reactions.…”

mentioning

confidence: 99%

Synthesis and Biological Evaluation of Cajaninstilbene Acid and Amorfrutins A and B as Inhibitors of the Pseudomonas aeruginosa Quorum Sensing System

Zeng

Huang

et al. 2018

J. Nat. Prod.

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The quorum sensing (QS) system inhibitors of Pseudomonas aeruginosa are thought to attenuate bacterial pathogenicity and drug resistance by inhibiting biofilm formation and the production of virulence factors. In this study, a synthetic approach to the natural products cajaninstilbene acid (1) and amorfrutins A (2) and B (3) has been developed and was characterized by the Heck reaction, which was used to obtain the stilbene core and a Pinick oxidation to give the O-hydroxybenzoic acid. The biological activities of these compounds against the P. aeruginosa quorum sensing systems were evaluated. Amorfrutin B (3) showed promising antibiofilm activity against P. aeruginosa PAO1 with a biofilm inhibition ratio of 50.3 ± 2.7. Three lacZ reporter strains were constructed to identify the effects of compound 3 on different QS systems. Suppression efficacy of compound 3 on the expression of lasB-lacZ and pqsA-lacZ as well as on the production of their corresponding virulence factors elastase and pyocyanin was observed.

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“…The resulting sulfenate could then enter in a classical catalytic cycle, through a ligand substitution step, and furnish, after reductive elimination, the anticipated aryl sulfoxide 2 . Additional features would include (i) a straightforward access to the precursors 1 ,4 with respect also to enantiopure substrates, from readily available sulfur‐based reagents such as the parent thiols or tert ‐butyl tert ‐butanethiosulfinate (Ellman’s thiosulfinate), and (ii) compatibility with a weak inorganic base (p K a value of about 6–7 for sulfenic acid)5b,17 and a stoichiometric amount of the electrophile. The overall sequence is however quite challenging.…”

Section: Optimization Of Cross‐coupling Conditions With Sulfenate Prementioning

confidence: 99%

tert‐Butyl Sulfoxides: Key Precursors for Palladium‐Catalyzed Arylation of Sulfenate Salts

et al. 2015

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Thep resent report describesa ne fficient and cleang eneration of sulfenate salts (R 1 SO À )b y pyrolysis of readilya vailable tert-butyl sulfoxides to give sulfenic acids (R 1 SOH) andt raceless isobutene,f ollowed by hydrogen abstraction with aw eak inorganicb ase (K 3 PO 4 ). Ther elevance of this process wase xemplified through an in situ palladiumcatalyzed cross-coupling reactionw ith aryl halides/ triflates leading to aryl sulfoxides.T he operationally simple C À Sb ond-forming protocold eveloped uses Pd(dba) 2 as catalyst and Xantphos as ligandi nt oluene or at oluene/H 2 Om ixture.F urther extensions include the use of di-tert-butyl sulfoxide as an equivalentf or sulfurm onoxide dianion (SO 2À )a nd the development of diastereoselective versionsi n the [2.2]paracyclophane and biaryl series.

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A New Role for Sulfenate Anions: Organocatalysis

Cited by 15 publications

References 12 publications

Density Functional Determination of the Energetics of the Formation of trans‐Stilbene Catalyzed by Sulfenate Anions

Density Functional Determination of the Energetics of the Formation of trans‐Stilbene Catalyzed by Sulfenate Anions

Synthesis and Biological Evaluation of Cajaninstilbene Acid and Amorfrutins A and B as Inhibitors of the Pseudomonas aeruginosa Quorum Sensing System

tert‐Butyl Sulfoxides: Key Precursors for Palladium‐Catalyzed Arylation of Sulfenate Salts

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