- Allylation and cyanation of aza-aromatics activated by chloroformate and a catalytic amount of iodine
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Allyltrimethylsilane and trimethylsilyl cyanide undergo smooth addition to N-acylated quinolines in the presence of a catalytic amount of iodine to afford 2-allyl- and 2-cyano-1,2-dihydroquinoline derivatives, respectively in good yields with high chemo- and regioselectivity. A variety of functional groups such as alkyl, alkoxy, halo, and nitro functionalities are tolerated under the reaction conditions.
- Yadav,Reddy,Srinivas,Sathaiah
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p. 3489 - 3492
(2007/10/03)
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- Mechanism of Reaction of 2-Ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ) with Nucleophiles and its Crystal Structure
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Hydrolysis of the title compound (1) occurs via reaction of the ptrotonated species (16) with H2O or HO(-).The high basicity of (1) a of (1H+) is 4.22>, which is necessary for high reactivity, is shown by analogues with 2-aryloxy- or 2-alkoxy-substituents, but not by 2-cyano-compounds or by 3,4-dihydroquinolines (10). 1-Aryl- or 1-alkyl-oxycarbonyl-substituents have the largest effect on reactivity a of (14H+) is 2.3 and its rate of reaction is increased 160-fold relative to (1H+)> suggesting that reaction of nucleophile initially occurs at this site.Both acetate and amine (trifluoroethylamine) buffers react with (1) by similar mechanisms involving reaction between (1H+) and either AcO(-) or free amine; the reaction-rate-pH profiles are 'bell-shaped.' A new mechanism for the reaction of (1) as a reagent to promote peptide synthesis is suggested.Crystals of (1) are monoclinic, space group P21/n, with Z = 4 in a unit cell of dimensions a = 12.608(2), b = 7.644(1). c = 13.374(2) Angstroem, β = 99.06(2) deg.The structure was determined by direct methods from four-circle diffractometer data and refined to a final R value of 5.47percent from 1 490 observed reflections.
- Cremin, Denis J.,Hegarty, Anthony F.,Begley, Michael J.
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p. 412 - 420
(2007/10/02)
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