Crimmins Michael T, Zuccarello J Lucas, McDougall Patrick J, Ellis J Michael
University of North Carolina at Chapel Hill, Department of Chemistry, Chapel Hill, NC 27599-3290, USA.
Chemistry. 2009 Sep 14;15(36):9235-44. doi: 10.1002/chem.200900777.
A highly convergent, enantioselective total synthesis of brevetoxin A is reported. The development of a [X+2+X] Horner-Wadsworth-Emmons/cyclodehydration/reductive etherification convergent coupling strategy allowed a unified approach to the synthesis of two advanced tetracyclic fragments from four cyclic ether subunits. The Horner-Wittig coupling of the two tetracyclic fragments provided substrates that were explored for reductive etherification, the success of which delivered a late-stage tetraol intermediate. The tetraol was converted to the natural product through an expeditious selective oxidative process followed by methylenation.
报道了一种高度收敛的、对映选择性全合成短裸甲藻毒素A的方法。[X+2+X]霍纳-沃兹沃思-埃蒙斯/环脱水/还原醚化收敛偶联策略的开发，使得能够采用统一的方法从四个环醚亚基合成两个高级四环片段。两个四环片段的霍纳-维蒂希偶联提供了用于还原醚化研究的底物，其成功得到了一个晚期四醇中间体。通过快速的选择性氧化过程，然后进行亚甲基化，将四醇转化为天然产物。
