我们报告一位将军,具有侧挂亲核试剂的未活化烯烃的分子内环异构化。反应在温和的条件下进行,并耐受醚,酯类,受保护的胺,缩醛,吡唑,氨基甲酸酯,和芳烃。它适合于N-,O-,以及C-亲核试剂,产生许多不同的杂环,包括,但不限于,吡咯烷,哌啶,恶唑烷酮,和内酯。使用苯并噻嗪并喹喔啉作为有机光催化催化剂和Co-salen催化剂消除了对化学计量氧化剂或还原剂的需要。我们展示了该方案在后期药物多样化和几种小型天然产物合成中的实用性。
We report a general, intramolecular cycloisomerization of unactivated olefins with pendant nucleophiles. The reaction proceeds under mild conditions and tolerates ethers, esters, protected amines, acetals, pyrazoles, carbamates, and arenes. It is amenable to N-, O-, as well as C-nucleophiles, yielding a number of different heterocycles including, but not limited to, pyrrolidines, piperidines, oxazolidinones, and lactones. Use of both a benzothiazinoquinoxaline as organophotocatalyst and a Co-salen catalyst obviates the need for stoichiometric oxidant or reductant. We showcase the utility of the protocol in late-stage drug diversification and synthesis of several small natural products.