Stereocontrolled Synthesis of Acyclic 1,3-Diols via Condensation of Tungsten−syn-π-Pentadienyl Complexes with Aldehydes. A New Prins Reaction via s-trans-Diene Cationic Intermediates
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Abstract
In the presence of BF(3).Et(2)O, condensation of CpW(CO)(2)(syn-pi-2-methoxycarbonylpentadienyl) with aldehydes generated tungsten-eta(4)-trans-diene cation in cold toluene, and hydrolysis of this salt afforded tungsten-pi-allyl-anti-1,3-diols in good yields. This new synthesis of anti-1,3-diols represents an atypical Prins reaction that is applicable to normal aldehydes. The anti/syn ratios of 1,3-diols increased with an increase in the size of the aldehydes. These anti-1,3-diols were transformed into various complex oxygen heterocycles based on two demetalations: (1) conversion to an allyl cation followed by nucleophilic attack and (2) condensation with aldehydes via its CpW(NO)Cl derivative, to give functionalized alpha-methylene butyrolactones. A semi-emperical calculation was performed to deduce the transition-state structure to rationalize the anti-stereoselectivity.
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