Cu-mediated C-2 chlorination of indoles was accomplished with copper(ii) chloride through the use of a directing pyrimidyl protection group. A highly regioselective manner can be achieved on a range of indole substrates with excellent functional group tolerance.

A method for Pd-catalyzed, aminoquinoline-directed arylation of vinylic C-H bonds with aryl iodides has been developed. This reaction represents a rare example of Pd-catalyzed vinylic C-H functionalization of unsubstituted acrylamide, allowing for the highly regio- and stereoselective preparation of Z-olefins. High tolerance to functional groups is observed with good yields and excellent selectivity. It offers a complementary synthetic method to traditional pathways for Z-olefins.

A direct C-2 methylation reaction of indoles bearing a readily removable N-2-pyrimidyl moiety as a site-specific directing group has been developed with a palladium catalyst. This reaction relied on the use of KF to promote efficient methylation. A moderate to good yield was achieved in a range of indole substrates.

No abstract

In this novel and alternative route to 2‐methylindoles, the removable 2‐pyrimidyl group is preferentially used as directing group.