Riveira Martín J, Diez Cintia M, Mischne Mirta P, Mata Ernesto G
Instituto de Química Rosario, Facultad de Ciencias Bioquímicas y Farmacéuticas , Universidad Nacional de Rosario-CONICET , Suipacha 531 , S2002LRK , Rosario , Argentina.
J Org Chem. 2018 Sep 7;83(17):10001-10014. doi: 10.1021/acs.joc.8b01378. Epub 2018 Jul 11.
The transition-metal-catalyzed [2 + 2 + 2]-cycloaddition of alkynes has become a powerful atom-economical strategy for aromatic ring construction. Unfortunately, the control of the stereo-, regio-, and chemoselectivity of these processes is usually challenging, and these reactions can potentially lead to complex unuseful mixtures. While solid-phase chemistry has proven to be a successful tool for decreasing the number of cycloadducts formed and for facilitating the purification step, an integral use of the outcoming products in this complex reaction is described herein. By using an immobilized monoalkyne, the transition-metal-catalyzed [2 + 2 + 2]-cycloaddition with soluble 1,6-diyne-esters led to the simultaneous preparation of soluble and solid-supported phthalides, showing a new way to benefit from solid-phase synthetic methodologies.
过渡金属催化的炔烃[2 + 2 + 2]环加成反应已成为构建芳香环的一种强大的原子经济策略。不幸的是，控制这些反应的立体、区域和化学选择性通常具有挑战性，并且这些反应可能会产生复杂的无用混合物。虽然固相化学已被证明是减少环加成产物数量和促进纯化步骤的成功工具，但本文描述了在这种复杂反应中对所得产物的整体利用。通过使用固定化的单炔烃，过渡金属催化的与可溶性1,6-二炔酸酯的[2 + 2 + 2]环加成反应可同时制备可溶性和固相负载的邻苯二甲酸酯，这展示了一种从固相合成方法中获益的新途径。
