标题：Transition metal-free direct dehydrogenative arylation of activated C(sp(3))-H bonds: synthetic ambit and DFT reactivity predictions
作者：Lovato, Kaitlyn; Guo, Lirong; Xu, Qing-Long; Liu, Fengting; Yousufuddin, Muhammed; Ess, Daniel H.; Kurti, Laszlo; Gao, Hongyin
作者机构：[Guo, Lirong; Liu, Fengting; Gao, Hongyin] Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Shandong, 更多
通讯作者：Gao, HY;Kurti, L;Ess, DH;Ess, Daniel H
通讯作者地址：[Gao, HY]Shandong Univ, Sch Chem & Chem Engn, Key Lab Colloid & Interface Chem, Minist Educ, Jinan 250100, Shandong, Peoples R China;[Kurti, L]Rice Un 更多
摘要：A transition metal-free dehydrogenative method for the direct mono-arylation of a wide range of activated C(sp(3))-H bonds has been developed. This operationally simple and environmentally friendly aerobic arylation uses tert-BuOK as the base and nitroarenes as electrophiles to prepare up to gram quantities of structurally diverse sets (>60 examples) of alpha-arylated esters, amides, nitriles, sulfones and triaryl methanes. DFT calculations provided a predictive model, which states that substrates containing a C(sp(3))-H bond with a sufficiently low pK(a) value should readily undergo arylation. The DFT prediction was confirmed through experimental testing of nearly a dozen substrates containing activated C(sp(3))-H bonds. This arylation method was also used in a one-pot protocol to synthesize over twenty compounds containing all-carbon quaternary centers.