A Photocatalyzed Synthesis of Naphthalenes by Using Aniline as a Traceless Directing Group in [4 + 2] Annulation of Amino-benzocyclobutenes with Alkynes
Amino-benzocyclobutenes, Annulation, C-C cleavage, Photocatalysis, Substituted naphthalenes
We report a visible-light-promoted synthesis of substituted naphthalenes via [4 + 2] annulation of amino-benzocyclobutenes with alkynes. Amino-benzocyclobutenes, which are conveniently synthesized by [2 + 2] cycloaddition of arynes with ketenes followed by reductive amination, undergo regioselective opening of the cyclobutenyl ring to reveal a presumably distonic radical cation upon photooxidation by an excited iridium complex. The distonic radical cation undergoes the annulation with terminal and internal alkynes as well as diynes to afford structurally diverse naphthalenes. The regiochemistry of the annulation follows the pattern displayed in the addition of nucleophilic carbon radicals to alkynes. The aniline group plays a dual role in which it not only directs the initial photooxidation to generate the amine radical cation but also serves as a leaving group to complete aromatization.
Wang, Q., & Zheng, N. (2017). A photocatalyzed synthesis of naphthalenes by using aniline as a traceless directing group in [4 + 2] annulation of amino-benzocyclobutenes with alkynes. ACS Catalysis, 7(6), 4197-4201. doi:10.1021/acscatal.7b00716