"On Water" Direct Catalytic Vinylogous Aldol Reaction of Silyl Glyoxylates

The unique reactivity of water in the direct catalytic vinylogous aldol reaction of silyl glyoxylates is reported. With the hydrogen bonding networks from water, the unfavourable homogeneous reactions in organic solvents were severely suppressed, and the "On Water" relay chemistry for the vinylogous aldol reaction was realized in heterogeneous conditions (water as solvent), providing the desired α-hydroxysilanes with a quaternary carbon center in high yields. Moreover, the new insights on the role of water in biological systems were demonstrated.