Methylation of C(sp3)–H/C(sp2)–H Bonds with Methanol Catalyzed by Cobalt System,Organic Letters

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Methylation of C(sp3)–H/C(sp2)–H Bonds with Methanol Catalyzed by Cobalt System
Organic Letters ( IF 4.9 ) Pub Date : 2017-09-19 00:00:00 , DOI: 10.1021/acs.orglett.7b02462
Zhenghui Liu _{1,

2} , Zhenzhen Yang ₁ , Xiaoxiao Yu _{1,

2} , Hongye Zhang ₁ , Bo Yu ₁ , Yanfei Zhao ₁ , Zhimin Liu _{1,

2}

Affiliation

A highly efficient Co-based catalytic system, composed of a commercially available Co salt, a tetradentate phosphine ligand P(CH₂CH₂PPh₂)₃(PP₃), and a base (denoted as [Co]/PP₃/base), is developed for the methylation of C(sp³)–H and C(sp²)-H bonds using methanol as a methylating reagent. The Co(BF₄)₂·6H₂O/PP₃/K₂CO₃ catalytic system showed high catalytic activity for the methylation of C–H bonds in aryl alkyl ketones, aryl acetonitriles, and indoles, with wide substrate scope and good functional group tolerance, and methyl-substituted products were obtained in good to excellent yields at 100 °C. This cheap, readily available, and highly efficient Co-based catalytic system may have promising applications in methylation reaction using methanol.

中文翻译：

钴体系催化甲醇催化C（sp ³）–H / C（sp ²）–H键的甲基化

一种高效的钴基催化体系，由市售的钴盐，四齿膦配体P（CH ₂ CH ₂ PPh ₂）₃（PP ₃）和碱（表示为[Co] / PP ₃ / base）组成），用于使用甲醇作为甲基化试剂对C（sp ³）–H和C（sp ²）-H键进行甲基化。Co（BF ₄）₂ ·6H ₂ O / PP ₃ / K ₂ CO ₃催化体系对芳烷基酮，芳基乙腈和吲哚中CH键的甲基化反应具有很高的催化活性，具有广泛的底物范围和良好的官能团耐受性，在100°C条件下获得的甲基取代产物的收率好至极好C。这种便宜，容易获得且高效的Co基催化体系在使用甲醇的甲基化反应中可能具有广阔的应用前景。

更新日期：2017-09-19

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