Ketones quinolinyl

An example of a C-H bond activation process that employs this strategy is found in the pioneering work by Suggs et al. Specifically, Rh(I)-promoted activation of an a-C-C bond to ketone in 8-quinolinyl ketone 12 takes place via formation of a stable five-membered ring acylrhodium(III) complex (Scheme 3a) [18,19]. Examples of chelation-assisted C-C bond activation processes are foimd in reactions of the bidentate pincer-type compound 13 [20] (Scheme 3b) and ortho-a.cyl 2-phenyloxazole derivative 14 [21] (Scheme 3c). 

Keywords 8-Acylquinoline 8-Quinolinyl ketone All-carbon quaternary centers Bond insertion Carboacylation Carbon-carbon bond activation Chelation Cyclometalation Directed metalation Directing group Metallacycle Oxidative addition Rhodium catalyst... 

This rhodium-mediated C-C=0 activation was also used in the catalytic conversion of 8-quinolinyl ketones bearing a hydrogen at Cp, such as 8, into... 

Both vinyl- and aryl triflates have been cross-coupled with 2-furylzinc chloride [26-28]. Since vinyl triflates are easily obtained from the corresponding ketones, they are useful substrates in Pd-catalyzed reactions. In the following example, a Negishi coupling of 2-furylzinc chloride and indol-5-yl triflate (22) provided an expeditious entry to 2-(5 -indolyl)furan (23). Protection of the NH in the indole ring was not required. A similar reaction was successful with pyridyl- and quinolinyl triflates. 

KETONE, DIETHYLAMINO(7,8,9,10-TETRAHYDRO-ll-6H-CYCLOHEPTA(b)QUINOLINYL) see TCOlOO KETONE, 3,5-DIIODO-4-HYDROXYPHENYL 2,5-DIMETHYL-3-FURYL see DNF450 KETONE, 3,5-DIIODO-4-HYDROXYPHENYL 2-ETHYL-3-BENZOFURANYL see E1D200 KETONE, 3,5-DIIODO-4-HYDROXYPHENYL 5-ETHYL-2-FURYL see EID250 KETONE, 3,5-DIIODO-4-HYDROXYPHENYL 2-FURYL see DNF500 KETONE, DIMETHYL see ABC750 KETONE, 5-DIMETHYLAMINO-3-INDOLYL PHENYL see DOU700... 

Solubility determinations were used to characterize the polymorphism of 3-(((3-(2-(7-chloro-2-quinolinyl)-( )-ethenyl)-phenyl)-((3-dimethylamino-3-oxopropyl)-thio)-methyl)-thio)-propanoic acid. " The solubility of Form II was found to be higher than that of Form I in both isopropyl alcohol (IPA, solubility ratio equal to 1.7 over the range of 5-55°C) and methyl ethyl ketone (MEK, solubility ratio equal to 1.9 over the range of 5-55°C), indicating that Form I is the thermodynamically... 

Scheme 11.6 Chelation-assisted C—C bond cleavage of an 8-quinolinyl alkyl ketone.

A7-(Heteroarenesulfonyl)prolinatnides give up to 96% ee in aldol reactions of acetone with aryl trihalomethyl ketones (halo = F, Cl). An X-ray structure of the quinolinyl case (51) indicates it to be significantly pre-organized by hydrogen bonding. The reaction also works with NH imine derivatives of the aryl ketone in a Mannich-type... 

Reactions with compounds 7e-h were made catalytic using higher temperature (100°C), longer reaction time (48 h), and 6 atm of ethylene pressure (Scheme 9) [26]. Substrate 7e yielded 8-quinolinyl ethyl ketone 7b in 61% yield with the remaining material being imreacted starting material. The insufficient conversion... 

Suggs and Jun had determined that a homolysis-recombination mechanism was operative in the thermolysis of (S)-8-quinolinyl a-methoxybenzyl ketone 17 (see Scheme 7). An analogous cage-escape crossover experiment was performed on 3-methoxy-aiyl derivative 45 with 6-methyl-quinolinyl derivative 52 in order to probe the nature of the intermediates (Scheme 19). Both substrates underwent complete conversion to their respective product (53 and 54) without detection of crossover products 55 or 33. It is therefore unlikely that this transformatiOTi proceeds through a radical mechanism. 

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