Tert-butylthiol

Without question, the most significant advance in the use of sulfur-centered nucleophiles was made by Shibasaki, who discovered that 10 mol% of a novel gallium-lithium-bis(binaphthoxide) complex 5 could catalyze the addition of tert-butylthiol to various cyclic and acyclic meso-epoxides with excellent enantioselectiv-ities and in good yields (Scheme 7.11) [21], This work builds on Shibasaki s broader studies of heterobimetallic complexes, in which dual activation of both the electrophile and the nucleophile is invoked [22]. This method has been applied to an efficient asymmetric synthesis of the prostaglandin core through an oxidation/ elimination sequence (Scheme 7.12). 

Beilstein Handbook Reference) BRN 0505947 EINECS 200-890-2 HSDB 1611 t-Butyl mercaptan tert-Butanethiol tert-Butyl mercaptan tert-Butylthiol tertiary-Butyl mercaptan. Has skunk-like odor. Used as additive to natural gas for leak detection. Liquid mp = -0.5° bp = 64.3° d = 0.7943 soluble in organic solvents, insoluble in H2O. Lancaster Synthesis Co. Mallinckrodt Inc. Sigma-Aldrich Fine Chem. 

Once in hand, 100 may be used in multitudinous ways. Dreatment with a thiol (both aliphatic and aromatic ones having been employed) in the presence of potassium hydride in tetrahydrofuran (THE) solution affords the corresponding bis(thioethers) 142 in high yield [94] (Eq. (26)). Dichloroacetylene behaves as a very electrophilic compound which is readily attacked even by bulky nucleophiles (with tert-butylthiol the product 142 is obtained in 98% yield) [95] ... 

Working reagent A. Add 2.3 pL of tert-butylthiol to 1 mL of OPA solution and mix well. Protect this solution fi-om light and air by using amber-colored boro-silicate vials capped by a septum (thiols smell ). Prepare fresh every day. 

In a much simpler system, the outcome of a thioacetate Mitsunobu on a series of hydroxythiol derivatives depended on the nucleophilicity of the neighboring thiol group.Thus, the tert-butylthiol compound 248 gave the trans compound 249 via an intermediate episulfonium ion, whereas the corresponding Boc or acetyl protected thiols 250 gave the desired cis derivatives 251. 

As a specific example, 4-chlorobutanol 18 and the /7-tert-butylthiol 19, by refluxing with sodium hydroxide (2 hours), gave the thioalcohol (20, 85%), which by treatment with chlorosulfonic acid (one equivalent) in dichloromethane, followed by vacuum distillation at 70 °C, afforded the sulfonium salt (21, 80%) (Scheme 2). ... 

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