Department of Chemistry , Massachusetts Institute of Technology , Cambridge , Massachusetts 02139 , United States.
J Am Chem Soc. 2018 Apr 18;140(15):5057-5060. doi: 10.1021/jacs.8b02568. Epub 2018 Apr 6.
We show that a chiral copper hydride (CuH) complex catalyzes C-C bond-forming dearomatization of pyridines and pyridazines at room temperature. The catalytic reaction operates directly on free heterocycles and generates the nucleophiles in situ, eliminating the need for stoichiometric preactivation of either reaction partner; further, it is one of very few methods available for the enantioselective 1,4-dearomatization of heteroarenes. Combining the dearomatization with facile derivatization steps enables one-pot syntheses of enantioenriched pyridines and piperidines.
我们证明手性铜氢（CuH）配合物可在室温下催化吡啶和哒嗪的 C-C 键形成去芳构化反应。该催化反应可直接在游离杂环上进行，并原位生成亲核试剂，无需对任一反应伙伴进行化学计量的预活化；此外，它是少数几种可用于对杂芳烃进行对映选择性 1,4-去芳构化的方法之一。将去芳构化与易衍生化步骤相结合，可实现对映富集的吡啶和哌啶的一锅合成。
