I. DIELS-ALDER REACTIONS OF TRIMETHYL CYCLOPENTADIENYL STANNANE. II. PREPARATION AND DIELS-ALDER REACTIONS OF VINYLSULFOXIMINES.
AuthorREINEKE, KARL EDWARD, II.
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PublisherThe University of Arizona.
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AbstractIn Part 1, the Diels-Alder adducts of trimethyl cyclopentadienylstannane (I.3) with maleic anhydride and fumaronitrile are prepared in 61% yield. The molecular structure of the adduct with maleic anhydride (1.6) is unequivocally established as 7-syn-trimethy1stannyl-endo- bicyclo[2.2.1]hept-5-enyl-2,3-dicarboxy1ic anhydride by single crystal X-ray structure analysis. In Part II, the high yield preparation of some new S-a1ky1-Saryl- N-p-toluenesu1fonylsu1foximines, by ruthenium tetroxide oxidation of the corresponding su1filimine, is described. Dehydrochlorination of S-chloroethy1-N-p-toluenesu1fonyl-S-p-toly1su1foximine and its S-phenyl analog with triethylamine gives the previously unknown N-p-to1uenesu1fony1- S-p-to1y1-S-viny1sulfoximine (II.17) and its S-phenyl analog. The Diels-Alder reaction of II.17 with a variety of 1,3-dienes and the known N-phtha1imido-S-p-tolyl-vinylsu1foximine (11.14) and the previously unreported S-p-nitropheny1-N-phtha1imido-viny1su1foximine (11.39) with cyclopentadiene are described. All of the reactions give mixtures of the possible adducts. The configuration of the major diastereomer (II.19d) of the adducts of II.14 with cyclopentadiene is known from a single crystal X-ray structure analysis. The structures of the other adducts are determined by ¹H NMR spectroscopic analysis. Chemical correlation of II.19d with the adducts of II.17 with cyclopentadiene confirm the assignment made by ¹H NMR. A competition Die1s-Alder reaction between II.17 and p-toly1-viny1sulfone shows that the vinylsulfoximine is more reactive. Sodium amalgam reduction of the cyclohexadienyl adducts of II.17 gives bicyclo[2.2.2Joctene and hydrazine in allyl alcohol reduction of adduct II.19d gives the corresponding sulfoxide II.20d.