Kellogg School of Science and Technology at The Scripps Research Institute, The Scripps Research Institute, Scripps Florida, Jupiter, Florida 33458, USA.
J Am Chem Soc. 2012 Jan 18;134(2):1352-6. doi: 10.1021/ja2105703. Epub 2011 Dec 14.
A de novo synthesis of substituted pyridines is described that proceeds through nucleophilic addition of a dithiane anion to an α,β-unsaturated carbonyl followed by metallacycle-mediated union of the resulting allylic alcohol with preformed trimethylsilane-imines (generated in situ by the low-temperature reaction of lithium hexamethyldisilazide with an aldehyde) and Ag(I)- or Hg(II)-mediated ring closure. The process is useful for the convergent assembly of di- through penta-substituted pyridines with complete regiochemical control.
描述了一种通过二硫杂环戊烷阴离子对α,β-不饱和羰基的亲核加成，然后通过金属环介导的方式将生成的烯丙醇与预形成的三甲基硅烷亚胺（通过低温反应由六甲基二硅氮烷与醛原位生成）进行偶联，最后在 Ag(I)或 Hg(II)介导下进行环化反应，从而实现取代吡啶的从头合成。该方法在完全区域化学控制的条件下，可用于二取代至五取代吡啶的收敛性组装。
