Abstract
AbstractAryl 3‐ and 4‐pyridyl sulfoxides undergo ligand exchange in reactions with aryl Grignard reagents to generate 3‐ and 4‐pyridyl Grignard reagents, which, upon treatment with aldehydes or ketones, give the corresponding addition products in moderate‐to‐good yields. The mechanism for the exchange reaction was investigated by treating optically active 3‐ and 4‐pyridyl p‐tolyl sulfoxides with a phenyl Grignard reagent. Inversion of the configuration of the sulfur atom was the stereochemical result of the reactions. In the reactions of phenyl 2‐pyridyl sulfoxide with Grignard reagents, the leaving ability of the 2‐pyridyl group competes with that of the phenyl group. Both the experimental and MO calculated enthalpy values for deprotonation of α‐, β‐, and γ‐protons of pyridine in the gas phase [1] are in accordance with the following order of the leaving abilities of aryl and pyridyl Grignard reagents: 4‐PyMgBr > 3‐PyMgBr » PhMgBr > p‐TolMgBr > 2‐PyMgBr.
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