College of Chemistry and Chemical Engineering Anyang Normal University , Anyang 455002, PR China.
Henan Province Key Laboratory of New Optoelectronic Functional Materials, Anyang Normal University , Anyang 455002, PR China.
Org Lett. 2017 Oct 6;19(19):5166-5169. doi: 10.1021/acs.orglett.7b02439. Epub 2017 Sep 15.
The first example of transition-metal-catalyzed ortho/meta-selective dual C-H functionalizations of arenes in one reaction is described. In this transformation, ortho-C-H chlorination and meta-C-H sulfonation of 2-phenoxypyri(mi)dines were achieved simultaneously under catalysis by [Ru(p-cymene)Cl]. The other reactant, namely, an arylsulfonyl chloride, played the role of both a sulfonation and chlorination reagent. More importantly, the arylsulfonyl chloride was also an oxidant in the process. Mechanistic studies indicated that six-membered ruthenacycles were the key intermediate in the reaction.
本文首次报道了首例在同一反应中过渡金属催化的芳环邻位/间位选择性双 C-H 官能化反应。在该转化中，[Ru(p-cymene)Cl]催化下，2-苯氧基吡啶并[mi]哒嗪的邻位 C-H 氯化和间位 C-H 磺化可同时进行。另一种反应物，即芳基磺酰氯，同时扮演磺化和氯化试剂的角色。更重要的是，芳基磺酰氯在该过程中也是一种氧化剂。机理研究表明，六元钌环是反应的关键中间体。
