Palladium-Catalyzed Transient Chirality Transfer and Atroposelective C-H Functionalization to Access Quaternary Stereocenters.

Although palladium-catalyzed asymmetric C-H functionalization and Heck reactions represents one of the most important synthetic strategies for the construction of quaternary stereocenters, developing the enantioselective version of Pd II -catalyzed carbopalladation-initiated cascade reactions still remains a formidable challenge. Herein, an unprecedent enantioselective [3+2] annulation of oxime ethers and alkynes has been developed, providing both spiro and nonspiro indenes bearing all-carbon quaternary stereocenters in good yields (up to 98 %) with excellent enantioselectivities (up to >99 % ee). This annulation is accomplished by merging the Pd II -catalyzed atroposelective C-H activation/double carbopalladation and the transient axial-to-central chirality transfer process, constituting the first successful example of catalytic chirality transfer strategy involving axially chiral styrene intermediate.