Cobalt-Catalyzed Formal [4+2] Cycloaddition of α,α′-Dichloro-ortho-Xylenes with Alkynes†
Corresponding Author
Prof. Dr. Kimihiro Komeyama
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)Search for more papers by this authorYuji Okamoto
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Search for more papers by this authorProf. Dr. Ken Takaki
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Search for more papers by this authorCorresponding Author
Prof. Dr. Kimihiro Komeyama
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)Search for more papers by this authorYuji Okamoto
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Search for more papers by this authorProf. Dr. Ken Takaki
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima City, Hiroshima 739-8527 (Japan)
Search for more papers by this authorThis work was partially supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Culture, Sports, Science and Technology of Japan. We are thankful for financial support from the Electronic Technology Research Foundation of Chugoku.
Abstract
A formal [4+2] cycloaddition of α,α′-dichloro-ortho-xylenes with various alkynes has been developed using a low-valent cobalt catalyst. The transformation has a wide substrate scope and high functional-group tolerance and led to 1,4-dihydronaphthalenes. The formed cycloadducts were easily aromatized with MnO2 under air. A mechanistic investigation suggests that the transformation proceeds through a benzyl cobaltation of alkyne, not the classical Diels–Alder reaction of ortho-quinodimethanes. This methodology provides a straightforward and streamlined access to linearly expanded π-conjugated aromatics.
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