Categories: C-H Bond Formation >
A catalytic reductive cleavage of C(sp2)- and C(sp3)-SMe bonds under ligandless conditions offers a wide scope and high chemoselectivity profile including challenging substrate combinations, allowing the design of orthogonal and site-selectivity approaches.
N. Barbero, R. Martin, Org. Lett., 2012, 14, 796-799.
With a molybdenum hexacarbonyl mediated desulfurization of thiols and disulfides, sulfhydryl groups of aryl, benzyl, primary and secondary alkyl thiols, and S-S single bonds of disulfides can be removed. This reaction tolerates many functional groups and is not affected by steric hindrance.
Z. Wang, Y. Kuninobu, M. Kanai, Synlett, 2014, 25, 1869-1872.
Nickel catalyzes a highly chemoselective cleavage of sp2-hybridized carbon-sulfur bonds of readily available aryldimethylsulfonium triflates to produce salt-free arylzinc triflates under mild conditions. The generated arylzinc reagents show both high reactivity and chemoselectivity in palladium-catalyzed and copper-mediated cross-coupling reactions.
K. Yamada, T. Yanagi, H. Yorimitsu, Org. Lett., 2020, 22, 9712-9718.
The reaction of 1-(methylthio)acetone with different nitriles in the presence of triflic anhydride gave 2-substituted 5-methyl-4-methylthio-1,3-oxazoles in good yield. The methylthio group at the C4 position can easily be removed with Raney nickel. 4-Methylsulfonyl derivatives were prepared by the oxidation of the MeS group with m-CPBA.
A. Herrera, R. Martinez-Alvarez, P. Ramiro, D. Molero, J. Almy, J. Org. Chem., 2006, 71, 3026-3032.