Highly Functionalized Cyclohexenes Derived from Benzene: Sequential Tandem Addition Reactions Promoted by Tungsten

The dihapto-coordination of benzene to the pi-basic fragment {TpW(NO)(PMe3)} (Tp = hydridotris(pyrazolyl)-borate) enhances the basicity of the arene ligand to the point that it can be protonated with a mild Bronsted acid (diphenylammonium triflate; pK(a) similar to 1). The resulting eta(2)-benzenium complex reacts with a wide range of nucleophiles including protected enolates, cyanide, amines, methoxide, and aromatic nucleophiles to form 5-substituted 3,4-eta(2)-1,3-cyclohexadiene complexes in good yield (42-70%). These coordinated dienes were successfully taken through a second protonation and nucleophilic addition with a similar scope of nucleophiles (54-80%). The resulting cis-3,4- and cis-3,6-disubstituted eta(2)-cyclohexene complexes were prepared with high regio- and stereo- control, as governed by the asymmetric nature of pi-allyl intermediates. In some cases, a diene linkage isomerization from 3,4-eta(2) to 1,2-eta(2) could be effected with a redox catalyst, and reactions of the latter species led to cis-3,5-disubstituted cyclohexene products exclusively. Oxidative decomplexation afforded the free cyclohexene products in moderate yield (37-68%). Additionally, when a single enantiomer of the chiral dearomatization agent was used, the elaborated cyclohexenes were able to be synthesized in enantioenriched forms (86-90% enantiomeric excess). Full characterization of 40 new compounds is provided that includes two-dimensional NMR, IR, electrochemical and in some cases crystallographic data.