Research Of 1, 4-Conjugate Addition And Relative Reactions

In this dissertation, much attention has been focused on the 1,4-conjugate addition of indole (donor) withα,β-unsaturated ketones (acceptor), the asymmetric 1,4-conjugate addition of Grignard regeants (donor) withα,β-unsaturated esters (acceptor), their relative reactions. The whole work is mainly composed of following three parts:Part I: we first reported 1,4-conjugate addition of indole withα,β-unsaturated ketones catalyzed by iodine, Ceric ammonium nitrate (CAN) or Toluene-4-sulfonic acid (PTSA) under mild conditions to give the desired products in high to excellent yields. Then we directed our studies to investigate the reaction of indole withα,β-unsaturated electron-deficient compounds 1-oxo-13c-alkyloxy-1,13c-dihydrodibenzo[a, kl]-xanthene catalyzed by CAN, the reaction of indole with 9H-xanthen-9-ol catalyzed by CAN or Indium Tris(dodecyl sulfonate), to afford a serials of indole derivatives as SN1 products.Part II: we studied the reactions of indole with carbonyl compounds such as aldehydes and isatins catalyzed by iodine under solvent-free conditions, CAN udner ultrasonic conditions, Ferric dodecyl sulfonate or Meldrum's acid under aqueous conditions to synthesis of bisindolyl derivatives. Then, we also studied the mechanism of the reaction of indole with isatin catalyzed by CAN under ultrasonic conditions via 1,4-addition of indole and synthesised a series of unsymmetrical bisindolyl derivatives.Part III: We first described the enantioselective addition of Grignard regeants toα,β-unsaturated esters using simple reaction procedures, employing commercially available chiral Tol-BINAP. The desiredβ-alkyl esters could be obtained in good yields and high enantioselectivities. We also described enantioselective addition of MeMgBr toα,β-unsaturated esters using simple revised reaction procedures. The futher work was exploring the mechanism of this reaction via NMR and mass study.