Access to 4-Alkenylated Coumarins via Ruthenium-Catalyzed Olefinic C-H Alkenylation of Coumarins with Modifiable and Removable Directing Groups.

ABSTRACT

The ruthenium-catalyzed activation of the C4 position of coumarins for coupling with acrylates was described using modifiable ketone as a directing group. The alkenylation reaction provided a direct approach to prepare previously inaccessible 4-alkenylated coumarins with operational simplicity and high atom-economy. This protocol also worked well with coumarin-3-carboxylic acids to unveil a rare instance of a tandem alkenylation/decarboxylation reaction. The potential value of this approach was further highlighted by the efficient synthesis of several heterocyclic fused coumarin derivatives.