113606-76-1Relevant academic research and scientific papers
Catalytic Carbon-Carbon Bond Activation of Saturated and Unsaturated Carbonyl Compounds via Chelate-Assisted Coupling Reaction with Indoles
Pannilawithana, Nuwan,Yi, Chae S.
, p. 5852 - 5861 (2020)
The chelate assistance strategy was devised to promote a highly regioselective catalytic C-C bond activation reaction of saturated and unsaturated carbonyl compounds. The cationic Ru-H complex 1 was found to be an effective catalyst for mediating the coupling reaction of 1,2-disubstituted indoles with α,β-unsaturated aldehydes and ketones, in which the regioselective Cα-Cβ activation of the carbonyl substrates has been achieved in forming the 3-alkylindole products. The analogous coupling reaction of indoles with saturated aldehydes and ketones directly led to the Cα-Cβ cleavage of the carbonyl substrates in forming the 3-alkylindole products. The coupling reaction of 1,2-dimethylinole with (E)-3-nonen-2-one and 2-propanol-d8 showed 20-22percent of deuterium incorporation to both α-and β-CH2 of the 3-alkylindole product. The coupling reaction of 1,2-dimethylinole with (E)-3-nonen-2-one exhibited the most significant carbon kinetic isotope effect on the α-carbon of the product (Cα = 1.046). The Hammett plot constructed from the reaction of 1,2-dimethylinole with a series of para-substituted enones p-X-C6H4CH=CHCOCH3 (X = OMe, Me, H, Cl, CF3) showed a modest promotional effect by an electron-donating group (ρ =-0.2 ± 0.1). Several catalytically relevant Ru-H species were detected by NMR from a stoichiometric reaction mixture of the Ru-H complex 1 with 1,2-dimethylindole and (E)-3-nonen-2-one in CD2Cl2. These results support a mechanism of the catalytic coupling reaction via conjugate addition of indoles to enones followed by the C-C bond activation and hydrogenolysis steps.
Reactions of Dimethyl Acetylenedicarboxylate with Indoles having Bulky 3-Substituents, and Further Reactions of Pyrroloindoles
Letcher, Roy M.,Choi, Michael C. K.,Wai, John S. M.
, p. 2629 - 2659 (2007/10/02)
The addition of dimethyl acetylenedicarboxylate to nine pyrroloindoles, and to nine N-methylindoles with bulky 3-substituents, has yielded twenty three new adducts.Their structures, elucidated mainly from spectroscopy which includes extensive diagnostic use of 13C-1H n.m.r. coupling constants, show several novel features, but all adducts are related to known adduct types.The results show that for relatively unstrained pyrroloindoles, the formation of an amino-ketone intermediate is still significant, but not dominant, that bulky 3-alkyl substituents of indoles can be eliminated to give 2-hydroxycarbazoles, and also that 3-phenyl groups appear to inhibit any reaction.
