The role of hypervalent intermediates in alkyl transfer reactions at sulfonium centers

Young, Paul R.; Ruekberg, Benjamin P.

doi:10.1016/0166-1280(89)87041-1

Cited by 5 publications

(1 citation statement)

References 28 publications

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“…14 In 1989, the Young group reported a series of kinetic studies that supported the formation of azasulfurane intermediates from sulfonium salts. 15 Theoretical studies from the Morokuma group 16 provided further support for the bipyramidal sulfurane intermediate in Oae and Furukawa's reaction, which allowed ligands to be placed at a dihedral angles of approximately 90°, thereby facilitating apical-axial ligand coupling through reductive elimination (either a three-center concerted coupling or a 1,2-shift followed by elimination). The Oae group also reported the homocoupling of 2-pyridyllithium by using thionyl chloride as a reagent.…”

Section: Synpacts Synlettmentioning

confidence: 97%

Unsymmetrical Heterocycle Cross-Couplings Enabled by Sulfur(IV) Reagents

Zhou

Tsien

Qin³

2020

Synlett

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Whereas metal-mediated cross-couplings find broad applications in syntheses of medicines, agrochemicals, and natural products, these powerful transformations have limited utility for Lewis basic substrates (e.g., heteroarenes), wherein basic functionalities coordinate to the metal center, hindering product formation. In this context, we have developed a transition-metal-free cross-coupling reaction mediated by sulfur(IV). This method leverages the ability of simple alkyl sulfinyl(IV) chlorides to form bipyramidal sulfurane complexes to drive a pseudo ‘reductive elimination’ process from the hypervalent sulfur atom, thereby readily providing unsymmetrical biheteroarenes.1 Introduction2 Historical Sulfurane(IV)-Mediated Couplings3 Unsymmetrical Heterocycle Cross-Couplings4 Conclusion

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Section: Synpacts Synlettmentioning

confidence: 97%

Unsymmetrical Heterocycle Cross-Couplings Enabled by Sulfur(IV) Reagents

Zhou

Tsien

Qin³

2020

Synlett

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New Aspects of Hypervalent Organosulfur Compounds

Furukawa

Sato

1999

Topics in Current Chemistry

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Inhibition of theClostridium perfringens phospholipase C hydrolysis of a thiophosphate analog of lysophosphatidylcholine by micelle‐bound ammonium and sulfonium cations

Young

Snyder

McMahon

1991

Lipids

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Cetyltrimethylammonium and n-octadecyldimethylsulfonium bromides inhibit the Clostridium perfringens phospholipase C-catalyzed hydrolysis of 1-S-phosphocholine-2-O-hexadecanoyl-1-mercapto-2-ethanol (1) at pH 7.5, 37 degrees C, mu = 0.15 with KCl. Mixed micelles containing 1 and either inhibitor are substrates for the enzyme and the fraction of activity remaining is a monotonic, but non-linear function of the mole fraction of inhibitor. Simple saturation kinetics are observed as the concentration of 1 is increased in mixed micelles containing a constant mole fraction of inhibitor. Inhibition constants for cetyltrimethylammonium and n-octadecyldimethylsulfonium bromides are 0.66 +/- 0.04 and 0.25 +/- 0.02 mM, respectively. The data suggest that the significant inhibition previously observed for soluble alkyldisulfonium salts (K50 for dodecamethylene-bis(dimethylsulfonium) bromide, 27 microM) is dependent upon bifunctional cationic interactions rather than hydrophobic binding.

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The role of hypervalent intermediates in alkyl transfer reactions at sulfonium centers

Cited by 5 publications

References 28 publications

Unsymmetrical Heterocycle Cross-Couplings Enabled by Sulfur(IV) Reagents

Unsymmetrical Heterocycle Cross-Couplings Enabled by Sulfur(IV) Reagents

New Aspects of Hypervalent Organosulfur Compounds

Inhibition of theClostridium perfringens phospholipase C hydrolysis of a thiophosphate analog of lysophosphatidylcholine by micelle‐bound ammonium and sulfonium cations

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