DiMartino Gianluca, Hursthouse Michael B, Light Mark E, Percy Jonathan M, Spencer Neil S, Tolley Malcolm
School of Chemical Sciences, University of Birmingham, Edgbaston, UK.
Org Biomol Chem. 2003 Dec 21;1(24):4423-34. doi: 10.1039/b311261f.
Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three gamma,gamma-difluorinated beta,gamma-enones, which reacted with either vinyllithium,2-lithio-2H-dihydropyran or another metallated haloalkene to afford substituted trans-1,2-divinylcyclohexanols of different degrees of stability. These intermediates underwent neutral thermal oxy-Cope rearrangements when heated in xylene in Ace tubes. The first-formed enols ketonised without loss of HF to afford a range of cyclodecenones in moderate to good yield; X-ray crystallography was used extensively for product characterisation. All substrates rearranged more rapidly than a cis/trans mixture of 1,2-divinylcyclohexanols.
金属化卤代烯烃被用于开环氧化合物，产率适中至良好。所得到的高烯丙醇进行斯文氧化反应，得到三种γ,γ-二氟代β,γ-烯酮，它们与乙烯基锂、2-锂代-2H-二氢吡喃或另一种金属化卤代烯烃反应，得到不同稳定性程度的取代反式-1,2-二乙烯基环己醇。这些中间体在二甲苯中于Ace管中加热时发生中性热氧-Cope重排。首先形成的烯醇在不损失HF的情况下酮化，以适中至良好的产率得到一系列环癸烯酮；广泛使用X射线晶体学对产物进行表征。所有底物的重排比1,2-二乙烯基环己醇的顺/反混合物更快。
