Synthesis of Sulfur Enriched Cyclohexenes via the Tungsten‐Promoted Dearomatization of a Phenyl Sulfone

Prior work with the dearomatization agent [WTp(NO)(PMe 3 )] (Tp = trispyrazolylborate) has demonstrated the ability to synthesize cis , cis −3,4,6 trisubstituted cyclohexenes from phenyl sulfones. Herein, the compatibility of these methods with sulfur nucleophiles was investigated for the synthesis of sp 3 ‐enriched thioether‐ and thioacetate‐functionalized cyclohexenes. Protonation of the WTp(NO)(PMe 3 )( η 2 ‐PhSO 2 Me) complex followed by addition of a sulfur nucleophile was only successful for a thioacetate salt. However, when the first nucleophile was an ester enolate, subsequent protonation and nucleophilic addition successfully yielded a range of cyclohexene complexes with thioacetate, thiol, and sulfonyl substituents. Oxidative decomplexation of these complexes liberated the corresponding cyclohexene products. This strategy was then applied to the synthesis of a thioglycolate ester functionalized tetrahydrophenanthridinone.