Shi Bin, Liu Jia-Bin, Wang Ze-Tian, Wang Liang, Lan Yu, Lu Liang-Qiu, Xiao Wen-Jing
CCNU-uOttawa Joint Research Centre, Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, 152 Luoyu Road, Wuhan, Hubei 430079, China.
Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.
Angew Chem Int Ed Engl. 2022 Jun 13;61(24):e202117215. doi: 10.1002/anie.202117215. Epub 2022 Apr 11.
Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present a new relay strategy merging Pd-catalyzed asymmetric [3+2] annulation with enyne-Cope rearrangement, providing a facile route to chiral 9-membered endocyclic allenes with high efficiency and enantioselectivity. Moreover, theoretical calculations and experimental studies were performed to illustrate the critical, but unusual Cope rearrangement that allows for the complete central-to-axial chirality transfer.
由于张力不利和手性复杂，手性内烯丙基的催化不对称合成在联烯化学中仍然是一个挑战。在此，我们提出了一种新的接力策略，将钯催化的不对称[3+2]环化反应与烯炔-Cope重排反应相结合，为高效、高对映选择性地合成手性9元内烯丙基提供了一条简便的途径。此外，还进行了理论计算和实验研究，以阐明关键但不寻常的Cope重排反应，该反应能够实现完全的中心到轴手性转移。
