Department of Biochemistry, The University of Texas Southwestern Medical Center, 5323 Harry Hines Boulevard, Dallas, TX, 75390-9038, USA.
Angew Chem Int Ed Engl. 2020 May 4;59(19):7372-7376. doi: 10.1002/anie.201915425. Epub 2020 Mar 17.
Despite the tremendous utilities of metal-mediated cross-couplings in modern organic chemistry, coupling reactions involving nitrogenous heteroarenes remain a challenging undertaking - coordination of Lewis basic atoms into metal centers often necessitate elevated temperature, high catalyst loading, etc. Herein, we report a sulfur (IV) mediated cross-coupling amendable for the efficient synthesis of heteroaromatic substrates. Addition of heteroaryl nucleophiles to a simple, readily-accessible alkyl sulfinyl (IV) chloride allows formation of a trigonal bipyramidal sulfurane intermediate. Reductive elimination therefrom provides bis-heteroaryl products in a practical and efficient fashion.
尽管金属介导的交叉偶联在现代有机化学中具有巨大的实用性，但涉及含氮杂芳环的偶联反应仍然是一项具有挑战性的任务 - 将路易斯碱性原子配位到金属中心通常需要高温、高催化剂负载等条件。在此，我们报告了一种硫（IV）介导的交叉偶联方法，可有效地合成杂芳基底物。向简单易得的烷基亚砜（IV）氯中加入杂芳基亲核试剂，可形成三角双锥硫烷中间体。从那里进行还原消除，可以以实用且高效的方式得到双杂芳基产物。
