Anhui Agricultural University, Hefei, Anhui 230036, China.
Shandong First Medical University, Jinan, Shandong 250117, China.
J Am Chem Soc. 2021 Nov 10;143(44):18380-18387. doi: 10.1021/jacs.1c09797. Epub 2021 Oct 27.
The pioneering nickel-catalyzed cross-coupling of C-O electrophiles was unlocked by Wenkert in the 1970s; however, the transition-metal-catalyzed asymmetric activation of aromatic C-O bonds has never been reported. Herein the first enantioselective activation of an aromatic C-O bond is demonstrated via the catalytic arylative ring-opening cross-coupling of diarylfurans. This transformation is facilitated via nickel catalysis in the presence of chiral -heterocyclic carbene ligands, and chiral 2-aryl-2'-hydroxy-1,1'-binaphthyl (ArOBIN) skeletons are delivered axially in high yields with high ee. Moreover, this versatile skeleton can be transformed into various synthetic useful intermediates, chiral catalysts, and ligands by using the CH- and OH-based modifiable sites. This chemistry features mild conditions and good atom economy.
温克特（Wenkert）在 20 世纪 70 年代开创了镍催化的 C-O 亲电试剂的交叉偶联反应；然而，芳香族 C-O 键的过渡金属催化不对称活化从未有过报道。在此，通过催化的芳基 C-O 键的区域选择性开环交叉偶联反应，首次实现了对芳基 C-O 键的对映选择性活化。该转化通过镍催化，在手性杂环卡宾配体的存在下促进，并且通过轴向高收率和高对映选择性提供手性 2-芳基-2'-羟基-1,1'-联萘（ArOBIN）骨架。此外，该多功能骨架可以通过使用基于 CH 和 OH 的可修饰位点转化为各种合成有用的中间体、手性催化剂和配体。该化学具有温和的条件和良好的原子经济性。
