Department of Chemistry, Graduate School of Science, Kyoto University , Sakyo-ku, Kyoto 606-8502, Japan.
J Am Chem Soc. 2014 Apr 30;136(17):6255-8. doi: 10.1021/ja5029028. Epub 2014 Apr 17.
Tuning the reactivity of arylpalladium intermediates enables control of catalytic arylative 5-exo and 6-endo cyclizations of alkynols. The two modes of cyclizations represent a rare example of controllable, regioselective difunctionalization of alkynes. The cyclizations are useful in offering a divergent synthesis of oxygen-containing heterocycles, which is of synthetic use for further derivatization. Formal synthesis of an hNK-1 receptor antagonist also showcases the utility of our arylative cyclization.
芳基钯中间体的反应性调控可实现对炔醇催化芳基化 5-endo 和 6-exo 环化的控制。这两种环化模式代表了炔烃可控、区域选择性双官能化的罕见实例。这些环化反应在提供含氧杂环的发散合成方面很有用，这对于进一步的衍生化具有合成用途。hNK-1 受体拮抗剂的形式合成也展示了我们芳基化环化的实用性。
