Catalysts that promote site-selective modification of polyfunctional molecules can be of significant utility in selective chemical synthesis.[1] Of particular importance are chiral catalysts that initiate enantioselective functionalization of polyoxygenated molecules [2]— entities commonly found among biologically active agents. Herein, we present methods for the enantioselective silylations [3] of acyclic and cyclic 1, 2, 3-triols [Eq.(1)]; the ...