An Extraordinary Photochemical Reaction of Pyrrole - A New Tool for Molecular Complexity

这项建议旨在探索我们实验室最近发现的一种强大的光化学反应。许多N-丁烯基取代的吡咯都可以通过特殊的光环加成/重排反应生成高分子复杂性的三环稠合氮杂环丙烷。早期的研究表明，只要吡咯在2-位上带有吸电子基团，反应序列就具有高度的取代耐受性。我们将通过考察各种环状和非环状烯烃的侧链取代的影响来研究环加成反应的范围。所得的氮丙啶本身将是反应性物质，并且应该经历许多有用的成键开环反应。一旦开发和理解的方法将被应用作为一个非常短的合成生物碱石斛碱的关键步骤。总的来说，本提案中的工作应有助于突出光化学和光化学技术在现代化学合成中的价值。

This proposal aims to explore a powerful photochemical reaction recently discovered in our laboratory. A variety of N-butenyl substituted pyrroles have been found to undergo an extraordinary photocycloaddition/rearrangement sequence to give tricyclic fused aziridines of high molecular complexity. Early studies have shown that as long as the pyrrole bears an electron withdrawing group on the 2-position the reaction sequence is highly tolerant of substitution. We will investigate the scope of the cycloaddition reaction by examining the effects of side chain substitution with a variety of cyclic and acyclic alkenes. The resulting aziridines will themselves be reactive species and should undergo a number of useful bond forming ring opening reactions. Once developed and understood the methodology will be applied as the key step in a very short synthesis of the alkaloid dendrobine. Overall the work in this proposal should serve to highlight the value of photochemistry and photochemical technology in modern chemical synthesis.