Addition of lithium aryl(tetraisopropoxy)titanates [ArTi(OPri)4 Li ] to , -unsaturated ketones proceeded with high enantioselectivity (up to 99% ee) in the presence of an excess amount of chlorotrimethylsilane and a rhodium catalyst (3 mol % Rh), generated from [RhCl(C2H4)2]2 and (S)-binap, in tetrahydrofuran at 20°C to give high yields of the corresponding silyl enolates as 1,4-addition produc...

Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C-O bonds in aryl ethers and C-S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number...

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal-organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and r...

Metal–metal bonds have been an interesting topic for many decades due to the fundamental studies in bonding properties, as well as potential applications in small molecule activation processes. Much of what is known about this area is mainly based on 2 and 3 row transitional metals. Understanding of the bonding behavior between first-row transition metals, however, is lacking due to the synthet...