Stereospecific 1,4‐Metallate Shift Enables Stereoconvergent Synthesis of Ketoximes

Reported herein is a stereospecific 1,4‐metallate rearrangement for single‐geometry ketoxime synthesis from oxime chlorides and arylboronic acids. This strategy exhibits broad substrate scope with excellent stereoselectivity under mild reaction conditions. In comparison with the conventional approaches, each configuration of unsymmetric diaryl oximes, as well as the thermodynamically less stable Z  isomer of aryl alkyl ketoximes can be selectively and exclusively obtained. The reactivities of unsymmetric diaryl oximes and the Z  isomer of aryl alkyl oximes, a class of underexplored molecules, enables efficient access to the corresponding isoquinolines, isoquinoline N ‐oxides, and amides having a single configuration.