Regio- and Stereocontrolled Nucleophilic Addition Reactions of a Phenylthio-Substituted Cyclohexadiene-Containing η⁴-Molybdenum Cationic Complex

Abstract

The reaction of a new cationic complex, [Cp-(CO) 2 Mo(η 4 -2-SPh-C 6 H 7 )] + PF 6 -(3), with carbon and sulfur nucleophiles was found to give in most cases the C-4 addition products 4 in good yield. The X-ray crystal structure of one of the addition products 4b confirms the regio-and stereochemistry of the reaction.

New Oxidative Demetalation Protocol for Molybdenum π-Complexes: Enantiocontrolled Synthesis of Unsaturated Ketones and Lactones

“…Iodo (or bromo) alkenes are formed by addition of halide to the intermediate cationic [CpMo(CO)(X)(η 3 -allyl)] + complex, trans to the metal . Poor regiocontrol results with unsymmetrically substituted η 3 -allyl complexes. 13a, When combined with suitable nucleophiles, iodo and bromo demetalations provide access to nucleophilic substitution products that are conceptually related to the CO/NO + ligand exchange protocol. 13b, Complexes containing a pendant nucleophile such as a carboxylate 13 or hydroxyl group produce cyclization products with high regio- and stereocontrol.…”