Schlimpen Fabian, Plaçais Clotilde, Starck Eliot, Bénéteau Valérie, Pale Patrick, Chassaing Stefan
Laboratoire de Synthèse, Réactivité Organique et Catalyse (LASYROC), Institut de Chimie, CNRS-UMR7177, Université de Strasbourg, 4 rue Blaise Pascal, Strasbourg 67070, France.
J Org Chem. 2021 Dec 3;86(23):16593-16613. doi: 10.1021/acs.joc.1c01893. Epub 2021 Nov 21.
The potential of copper(I)-zeolite catalysis was evaluated in the three-component KA-coupling mediated synthesis of α-tertiary propargylamines. Our archetypal copper(I)-doped zeolite Cu-USY proved to be efficient under ligand- and solvent-free conditions at 80 °C. Usable up to four times, this catalytic material enables the coupling of diverse ketones, alkynes, and amines with a broad functional group tolerance. A decarboxylative and a desilylative version, respectively, involving an alkynoic acid and trimethylsilylacetylene as alkyne surrogates, was also set up to bypass selectivity issues and/or to access α-tertiary propargylamines that are unattainable under standard KA conditions. Interestingly, the KA-type coupling reactions were successfully linked to other Cu-catalyzed reactions, thus resulting in sequential one-pot processes under full Cu-USY catalysis.
在α-叔炔丙胺的三组分KA偶联介导合成中评估了铜（I）-沸石催化的潜力。我们典型的铜（I）掺杂沸石Cu-USY在80°C无配体和无溶剂条件下被证明是有效的。这种催化材料可重复使用多达四次，能够使各种酮、炔烃和胺进行偶联，具有广泛的官能团耐受性。还分别建立了涉及炔酸和三甲基硅乙炔作为炔烃替代物的脱羧和脱硅版本，以绕过选择性问题和/或获得在标准KA条件下无法得到的α-叔炔丙胺。有趣的是，KA型偶联反应成功地与其他铜催化反应相连，从而在完全由Cu-USY催化的情况下实现了连续的一锅法过程。
