Site‐Selective C−H Allylation of Alkanes: Facile Access to Allylic Quaternary sp3‐Carbon Centers

• DOI: 10.1002/anie.202214519
• Publication Date: 2022-11-26T03:19:55Z
• Authors: Yong Yang; Shaopeng Liu; Shuang Li; Zhaohong Liu; Peiqiu Liao; Paramasivam Sivaguru; Ying Lu; Jiaojiao Gao; Xihe Bi
• Keywords: 01 natural sciences; 0104 chemical sciences

AbstractThe construction of allylic quaternary sp3‐carbon centers has long been a formidable challenge in transition‐metal‐catalyzed alkyl‐allyl coupling reactions due to the severe steric hindrance. Herein, we report an effective carbene strategy that employs well‐defined vinyl‐N‐triftosylhydrazones as a versatile allylating reagent to enable direct assembly of these medicinally desirable structural elements from low‐cost alkane feedstocks. The reaction exhibited excellent site selectivity for tertiary C−H bonds, broad scope (>60 examples and >20 : 1:0 r. r.) and good efficiency, even on a gram‐scale, making it a convenient alternative to the well‐known Trost–Tsuji allylation reaction for the formation of alkyl–allyl bonds. Combined experimental and computational studies were employed to unravel the mechanism and origin of site‐ and chemoselectivity of the reaction.