A synthetic route for the regioselective synthesis of polysubstituted quinones by the benzannulation and subsequent cross coupling reactions has been developed. Alkenyl chromium carbene complexes undergo regioselective benzannulation with Z-(trimethylsilyl)-1 -phenylethyne with oxidative workup to yield silyl quinones which upon iodination with ICI produce iodoquinones. Subsequent Stille's and Suzuki's cross coupling reactions of these iodoquinones yield polysubstituted quinones. The search for new synthetic approaches for the quinone functionality is a continuously growing area of investigation.' In fact, many polysubstituted quinones are incorporated in the structures of a variety of biologically natural products and some naturally occurring quinones2 are widely found in both plants and animals. However, the conventional synthetic approach to these highly substituted compounds involves the elaboration of the quinone precursors via electrophilic substitution and metalation-alkylation reaction which may subject to regiochemical problems. Therefore the regiocontrolled synthesis of highly substituted aromatic skeletons present a great synthetic challenge which is best met by the application of regioselective annulation strategies. The regioselective construction of quinones via the cyclobutenones-vinyl ketenes annulation . stratergy has been investigated mainly by Danheisers, Moore4 and Liebeskinds. Liebeskind further takes advantage of thermolysis of 4-alkyl-4-hydroxy-cyclobutenones in the presence of n-BugSnOMe to produce stannylquinones which undergo Stille's cross coupling reactions to yield polysubstituted quinones (eq 1). Do&, Semmelheckz and Wulff6 have employed the benzannulation of Fischer chromium carbene complexes with alkynes to synthesize quinones and the benzannulation, indeed, is a facile and regioselective entry to polysubstituted 1,4quinones (eq 2).g However, limitation exists. The substitutents of alkynes have to be symmetrical or substantially different in size otherwise regioisomeric mixtures are obtained.9 2004 K. S. (&AN and C