Asymmetric higher-order [10 + n] cycloadditions of palladium-containing 10π-cycloaddends. Issue 32 (1st August 2022)

• Record Type: Journal Article
• Authors: Li, Ao; Gao, Yang; Lu, Jian-Bin; Chen, Zhi-Chao; Du, Wei; Chen, Ying-Chun
• Is Part Of: Chemical science. Volume 13:Issue 32(2022)
• Page Start: 9265
• Page End: 9270
• Publication Date: 2022-08-01
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc02985e
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A type of π-allylpalladium complex-containing 10π-cycloaddend generated from 2-methylene-1-indanols under double activation of Pd(0) and phosphoric acid undergoes asymmetric higher-order [10 + 2] cycloadditions with diverse activated alkenes. Abstract : We uncovered an asymmetric higher-order [10 + 2] cycloaddition reaction between diverse activated alkenes and a new type of π-allylpalladium complex-containing dipole-type 10π-cycloaddend, which was generated in situ from 2-methylene-1-indanols via a dehydrative insertion and deprotonation strategy under double activation of Pd(0) and phosphoric acid. A similar strategy was applied to an asymmetric higher-order [10 + 8] cycloaddition reaction or [10 + 4] cycloaddition reaction by using a heptafulvene derivative or a cyclic enone, respectively, as the acceptor. A variety of polycyclic frameworks imbedding an indene core were generally furnished in moderate to excellent yields with high levels of enantioselectivity by employing a newly designed chiral phosphoramidite ligand.