2,3-Dihydrobenzofurans were achieved via a 1,6-conjugated addition-mediated [4 + 1] annulation of ortho-hydroxyphenyl-substituted para-quinone methides in high yields with high diastereoselectivity.

Transition-metal-catalyzed tandem Heck/carbonylation reaction has emerged as a powerful tool for the synthesis of structurally diverse carbonyl molecules, as well as natural products and pharmaceuticals. However, the asymmetric version was rarely reported, and remains a challenging topic. Herein, we describe a palladium-catalyzed asymmetric tandem Heck/carbonylation desymmetrization of cyclopentenes. Alcohols, phenols and amines are employed as versatile coupling reagents for the construction of multifunctional chiral bicyclo[3.2.1]octanes with one all-carbon quaternary and two tertiary carbon stereogenic centers in high diastereo- and enantioselectivities. This study represents an important progress in both the asymmetric tandem Heck/carbonylation reactions and enantioselective difunctionalization of internal alkenes.

Ap alladium-catalyzed asymmetric reductive Heck reaction of unactivated aliphatic alkenes,w ith eliminable b-hydrogen atoms,h as been realized for the first time.A series of optically active bicyclo[3.2.1]octanes bearing chiral quaternary and tertiary carbon stereocenters were obtained in good yields with excellent enantioselectivities,e xhibiting good functional-group tolerance and scalability.M oreover,d euterated optically active bicyclo[3.2.1]octanes were also obtained in high efficiency.

A dearomative coupling of β-naphthols with alkynes via Pd hydride catalysis has been developed. This redox-neutral strategy provides a straightforward platform to access diverse naphthalenones bearing congested quarternary stereocenters with excellent atom and step economy since no leaving groups are needed to preinstall on the allylic reagents. The overall utility of this protocol is exemplified by broad functional group compatibility and gram-scale capacity.

Herein, we disclose a strategy for the asymmetric dearomatization of N-arylacyl indoles via a palladium-catalyzed tandem Heck/carbonylation, leading to an array of indoline-3carboxylates bearing vicinal C2-aza-quaternary and C3 tertiary stereocenters in high yields and excellent enantio-and diastereoselectivities. This study is an important advance in the field of asymmetric carbonylation and enantioselective dearomatization reactions.

A palladium‐catalyzed asymmetric reductive Heck reaction of unactivated aliphatic alkenes, with eliminable β‐hydrogen atoms, has been realized for the first time. A series of optically active bicyclo[3.2.1]octanes bearing chiral quaternary and tertiary carbon stereocenters were obtained in good yields with excellent enantioselectivities, exhibiting good functional‐group tolerance and scalability. Moreover, deuterated optically active bicyclo[3.2.1]octanes were also obtained in high efficiency.