Stereochemistry of the silylcarbinol to silyl ether rearrangement

Abstract

It is shown that optically active methyl-α-naphthylphenylsilyldiphenylcarbinol and optically active methyl- α naphthylphenylsilylmethylphenylcarbinol undergo highly stereo-selective rearrangements to the isomeric silyl ethers. Both rearrangements involve retention of configuration at the asymmetric silicon center. The silylmethylphenylcarbinol is also shown to undergo retention of configuration with complete stereoselectivity at the asymmetric carbon center, regardless of the catalyst or solvent employed. The use of nuclear magnetic resonance for determining the proportions of the diastereomers is described, as are the syntheses of a number of asymmetric silicon compounds.