Jh. Bailey et al., SYNTHESIS AND DIELS-ALDER REACTIONS OF THIOISOBENZOFURANS, Journal of the Chemical Society. Perkin transactions. I, (5), 1995, pp. 589-592
Anions prepared by deprotonation of benzofused thionolactones reacted
with alkylating agents preferentially on sulfur. The resulting isobenz
ofurans underwent Diels-Alder reactions with dienophiles. This chemist
ry was developed as a one-pot procedure for the synthesis of bridged p
recursors of polycyclic aromatic compounds. The structure of one of th
e adducts, dimethyl endo-1-methylsulfanyl-8-phenyl-11-oxatricyclo[6.2.
1.0(2,7)] Undeca-2,4,6-triene-9.10-dicarboxylate 5a, was determined b
y single-crystal X-ray diffraction. The versatility of this approach w
as extended by lithiation of the intermediate anion whereby alkylation
introduced a further substituent on the aromatic nucleus. This method
ology may be appropriate for the synthesis of anti-tumour prodrugs.