Diastereoselective Construction of All-Carbon Quaternary Stereocenters via Intramolecular Oxidative Cross-Coupling Reaction

Abstract

The formation of sterically hindered C-C bond represents a great challenge in modern synthetic organic chemistry. A particularly challenging issue is the construction of all-carbon quaternary stereocenters. Herein, a ceric ammonium nitrate (CAN)-mediated intramolecular oxidative cross-coupling of silyl ethers for direct construction of valuable polycyclic scaffolds is described. The reaction enables sterically congested vicinal all-carbon quaternary and tertiary stereocenters to be installed diastereoselectively. The developed method provides a concise and efficient approach for ligation of two different segments through a compact C-C bond formation, which has potential applications in the synthesis of complex molecules as well as sterically congested natural products.

Recent Advances in the Oxidative Coupling Reaction of Enol Derivatives

“…前面提到利用双烯醇硅醚可以实现把分子间的反 应变成分子内的反应 [34][35][36][37][38][39] , 该合成策略在天然产物全合 成中具有重要的意义. 2018 年, Thomson 等报道了利用 双烯醇硅醚化合物分子内交叉氧化偶联反应来高效构 建分子中 C-C 键, 并成功实现了海洋二萜类天然产物 (＋)-7,20-diisocyanoadociane 的形式全合成.…”