Tran Hai N, Nguyen Chau M, Koeritz Mason T, Youmans Dustin D, Stanley Levi M
Department of Chemistry, Iowa State University Ames IA 50011 USA
Chem Sci. 2022 Aug 12;13(39):11607-11613. doi: 10.1039/d2sc01716d. eCollection 2022 Oct 12.
Direct coupling of unactivated alcohols remains a challenge in synthetic chemistry. Current approaches to cross-coupling of alcohol-derived electrophiles often involve activated alcohols such as tosylates or carbonates. We report the direct arylative substitution of homoallylic alcohols catalyzed by a nickel-bisphosphine complex as a facile method to generate allylic arenes. These reactions proceed formation of an allylic alcohol intermediate. Subsequent allylic substitution with arylboroxine nucleophiles enables the formation of a variety of allylic arenes. The presence of -methoxyphenylboronic acid is crucial to activate the allylic alcohol to achieve high product yields.
在合成化学中，未活化醇的直接偶联仍然是一个挑战。目前用于醇衍生亲电试剂交叉偶联的方法通常涉及活化醇，如甲苯磺酸酯或碳酸酯。我们报道了一种由镍-双膦配合物催化的高烯丙醇直接芳基化取代反应，作为一种生成烯丙基芳烃的简便方法。这些反应通过形成烯丙醇中间体进行。随后用芳基硼酸酯亲核试剂进行烯丙基取代，能够形成多种烯丙基芳烃。对甲氧基苯基硼酸的存在对于活化烯丙醇以实现高产物收率至关重要。
