Sulfoxides are frequently used in organic synthesis as chiral auxiliaries and reagents to mediate a wide variety of chemical transformations. For example, diphenyl sulfoxide and triflic anhydride can be used to activate a wide range of glycosyl donors including hemiacetals, glycals and thioglycosides. In this way, an alcohol, enol or sulfide is converted into a good leaving group for subsequent...

Metal sulfide minerals are assumed to form naturally at ambient conditions via reaction of a metallic element with (poly)sulfide ions, usually produced by microbes in oxygen-depleted environments. Recently, the formation of mercury sulfide (β-HgS) directly from linear Hg(II)-thiolate complexes (Hg(SR)2) in natural organic matter and in cysteine solutions was demonstrated under aerated condition...

Para-Aminobenzoic acid is supported on silica gel via reaction of activated silica gel and p-aminobenzoic acid which is then converted to its manganese and cobalt salts. A mixture of the manganese and cobalt salts of the acid is used to catalyze allylic and benzylic alcohols to their corresponding carbonyl compounds in reasonable yields using oxygen or air. Reactions are clean and the catal...

The thermodynamics for the first electron transfer step for sulfide and oxygen indicates that the reaction is unfavorable as unstable superoxide and bisulfide radical ions would need to be produced. However, a two-electron transfer is favorable as stable S(0) and peroxide would be formed, but the partially filled orbitals in oxygen that accept electrons prevent rapid kinetics. Abiotic sulfide o...

Green fluorescent protein has revolutionized cell labeling and molecular tagging, yet the driving force and mechanism for its spontaneous fluorophore synthesis are not established. Here we discover mutations that substantially slow the rate but not the yield of this posttranslational modification, determine structures of the trapped precyclization intermediate and oxidized postcyclization state...

Dibenzyl sulfide was oxidized at the α-carbon to yield benzaldehyde in the presence of Pd(NO3)2. Oxygen itself could not oxidize the sulfide directly, instead the nitrato ligand of the palladium complex transferred oxygen to dibenzyl sulfide to form benzaldehyde. The X-ray crystal structure of the intermediate complex, cis[Pd(NO3)2{S(CH2C6H5)2}2], revealed that the nitrato ligand was unidentate...

The reaction of sulfur ylides with carbonyl compounds to give epoxides is an important synthetic method. This Account charts the recent advances in rendering this process both asymmetric and catalytic. Two catalytic methods have been developed: the first involving the reaction of a sulfide with an alkyl halide in the presence of a base and aldehyde and the second involving the reaction of a sul...

The synthesis of the title compound, C(12)H(15)BrN(2)OS, involves the reaction of 4-bromo-benzoyl chloride with potassium thio-cyanate in dry acetone, followed by condensation of 4-bromo-benzoyl isothio-cyanate with diethyl-amine. The carbonyl and thio-carbonyl bond lengths indicate that these correspond to double bonds. The short C-N bond lengths reveal the effects of resonance in this part of...

Microwave irradiation (2.45 GHz, 300-500 W) of N-(alkoxy)thiazole-2(3H)-thiones in low-absorbing solvents affords alkoxyl radicals, which were identified by (i) spin adduct formation (EPR-spectroscopy) and (ii) fingerprint-type selectivities in intramolecular additions (stereoselective synthesis of disubstituted tetrahydrofurans), beta-fragmentations (formation of carbonyl compounds), and C,H-a...