Development of odorless organosulfur reagents and asymmetric reaction using odorless thiols

Odorless organosulfur reagents were developed by increasing their molecular weights to suppress volatility. 1‐Dodecanethiol (4), dodecyl methyl sulfide (5), p‐heptylphenylmethanethiol (6), p‐dodecylbenzenethiol (7), p‐heptylbenzenethiol (8), 2‐dodecyl‐1,3‐propanedithiol (11), p‐octyloxyphenyl‐methanethiol (18b), and p‐octyloxybenzenethiol (19) are typical examples of the odorless thiols and sulfides. 6‐Morpholinohexyl thiol (15), methyl 6‐morpholinohexyl sulfide (16), and methyl 6‐morpholinohexyl sulfoxide (17) were also developed as separable reagents from reaction products by facile acid‐base extraction. In addition, p‐tetramethylsilylphenylmethanethiol (18) and p‐tetramethylsilylbenzenethiol (14) were synthesized as the odorless synthetic substitutes of benzyl mercaptan and benzenethiol, respectively. In a similar way, silylated diphenyl disulfide (26) and diselenide (27) were prepared as odorless disulfide and diselenide. Moreover, 10‐sulfanylisoborneol (1) was found to be an excellent chiral odorless substitute of hydrogen sulfide in Michael addition.