Studies in Organic Sulfur Compounds. VII.¹ Lithium Aluminum Hydride Reduction of Xanthates to Mercaptans. Synthesis of Substituted β-Mercaptoethanols

Synthesis and Asymmetric Diels−Alder Reactions of Enantiopure 3-(Alkylsulfinyl)-1-methoxy-1,3-butadienes

“…( S )-2-Mercapto-2-phenylethanol (1B). Dimethyldithiocarbamate 12 (5.6 g, 19.8 mmol) was slowly added to 1.5 g (40 mmol) of LiAlH 4 suspended in dry Et 2 O (60 mL) at 0 °C. Following the addition, the mixture was refluxed for 4 h. The reaction mixture was cooled at room temperature and LiAlH 4 carefully quenched by adding wet Et 2 O, H 2 O, finally HCl 3 N until pH 3 was measured.…”

[2, 3] Sigmatropic Rearrangements on Lithiation of Some Allyl Sulfides. Preliminary communication

“…Geraniol was converted into 0-geranyl S-methyl dithiocarbonate by successive treatment with butyllithium, carbon disulfide and methyl iodide. On distillation it rearranged to S-linalyl S-methyl dithiocarbonate (86%, based on geraniol), which was cleaved*) with lithium aluminium hydride [15] t o give 11 (75%). 2-Methylbut-3-en-2-thiol, from which 2 was made, was obtained by an analogous sequence.…”

Synthesis of an Amino‐Functionalized Model of the Fe‐Only Hydrogenase Active Site

“…The direct preparation of thiols from alkyl halides and metal sulfides should be facile, but in our hands direct methods gave only a moderate yield of di‐thiol 21. Indirect methods involving thiourea22 and xanthate derivatives23 are commonly utilised for the synthesis of thiols, but these intermediates have to be transformed to thiols by hydrolysis with base or by reduction with lithium aluminium hydride, which will react also with the ester group in compound 2 24. However, treatment of thioacetates with amines under mild conditions has recently been shown to give thiols in good yields 25, 26.…”