1,5-Dithiacyclooctane is shown to chemically react more efficiently and to remove singlet oxygen from solution more rapidly than either thiane or 1,4-dithiane. These unusual characteristics of the 1,5-dithiacyclooctane reaction were explored using ab initio quantum chemical methods. A large number of persulfoxides, thiadioxiranes, and hydroperoxy sulfonium ylides were located and their structur...

In the title compound, C(19)H(21)ClOS(2), the dithiane ring adopts a chair conformation. The dihedral angle between the benzene rings is 87.88 (4)°. In the crystal, inversion dimmers linked by pairs of C-H⋯O inter-actions occur.

In the title compound, C(22)H(26)OS(2), prepared from (-)-1R-cis-caronaldehyde, the 1,3-dithiane ring adopts a chair conformation. An intra-molecular O-H⋯S hydrogen bond influences the mol-ecular conformation. In the crystal, weak inter-molecular C-H⋯S and C-H⋯O hydrogen bonds link the mol-ecules into chains propagating along [010].

Two approaches to tetrahydro-[1H]-2-benzazepin-4-ones of interest as potentially selective, muscarinic (M(3)) receptor antagonists have been developed. Base promoted addition of 2-(tert-butoxycarbonylamino)methyl-1,3-dithiane with 2-(tert-butyldimethylsiloxymethyl)benzyl chloride gave the corresponding 2,2-dialkylated 1,3-dithiane which was taken through to the dithiane derivative of the parent...

An investigation on the stereoselective cascade sulfa-Michael/aldol reaction of nitroalkenes and commercially available 1,4-dithiane-2,5-diol to 3,4,5-substituted tetrahydrothiophenes, bearing a quaternary stereocenter, is presented. A secondary amine thiourea derived from (R,R)-1,2-diphenylethylamine was found to be the most effective catalyst when using trans-β-methyl-β-nitrostyrenes affordin...

We report a desymmetrization of cyclohexadienones by intramolecular conjugate addition of a tethered dithiane nucleophile. Mild reaction conditions allow the formation of diversely functionalized fused bicyclic lactones. The products participate in facially selective additions from the convex surface, leading to allylic alcohol derivatives.

A highly convergent, stereocontrolled total synthesis of the architecturally complex marine sponge metabolite (-)-enigmazole A has been achieved. Highlights include an unprecedented late-stage large-fragment Petasis-Ferrier union/rearrangement, a multicomponent Type I Anion Relay Chemistry (ARC) tactic, and a dithiane-epoxide union in conjunction with an oxazole-directed stereoselective reduction.

The [1,5]-Brook rearrangement proceeds efficiently in a series of hydroxyl dithiane substrates with sodium and potassium bases; less effective are lithium bases. That the mode of silyl migration is intramolecular was demonstrated by a crossover experiment. Finally, the tricomponent anion relay chemistry (ARC) coupling tactic was demonstrated employing the [1,5]-Brook rearrangement.