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In 2293, the location of Alpha Centauri in the Milky Way Galaxy was labeled in a star chart that was in Captain James T. Kirk's cabin aboard the USS Enterprise-A. (Star Trek VI: The Undiscovered Country, production art)
The location of Alpha Centauri (misspelled as "Alpha Centuri") identified in the "The Explored Galaxy" star chart placed it between the Tholian Assembly and Romulus. Both were identified in dialog from DS9: "Call to Arms" as being located in the Alpha Quadrant.