Abstract
Electrophilic P2Pt2+ complexes are shown to catalyze the regio- and diastereoselective oxidative cascade cyclization of poly-enes. The reactions are stereospecific with respect to the initiating alkenes geometry and suggest an all-chair, semiconcerted transition structure. Catalyst turnover after cyclization apparently occurs via β-hydride elimination and subsequent hydride abstraction (from P2Pt−H+) by added Trityl cation (in the form of trityl methyl ether or a resin version thereof) to regenerate the active P2Pt2+ state. One intriguing possibility is that the high regioselectivity observed in the β-H elimination is due to a regio-defining β-agostic resting state.
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