Face Selection in Claisen Rearrangements

Mukherjee, Ashis K.; Wu, Qianhong; Noble, W. J. Le

doi:10.1021/jo00091a010

Cited by 22 publications

(12 citation statements)

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“…To synthetize amides and thioamides, commercially available 1-adamantane carboxylic acid chloride 31 was used. An isomeric chloride of 2-adamantane carboxylic acid 32 was obtained starting from adamantan-2-one 33 according to previously published methods [68][69][70] including the synthesis of epoxide 34, its treatment with boron trifluoride etherate and subsequent oxidization (Scheme 1). 2-Adamantane carboxylic acid 35 was refluxed in thionyl chloride yielding chloride 32 quantitatively.…”

Section: Organic Synthesismentioning

confidence: 99%

The Development of Tyrosyl-DNA Phosphodiesterase 1 Inhibitors. Combination of Monoterpene and Adamantine Moieties via Amide or Thioamide Bridges

et al. 2019

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Eleven amide and thioamide derivatives with monoterpene and adamantine substituents were synthesised. They were tested for their activity against the tyrosyl-DNA phosphodiesterase 1 DNA (Tdp1) repair enzyme with the most potent compound 47a, having an IC50 value of 0.64 M. When tested in the A-549 lung adenocarcinoma cell line, no or very limited cytotoxic effect was observed for the ligands. However, in conjunction with topotecan, a well-established Topoisomerase 1 (Top1) poison in clinical use against cancer, derivative 46a was very cytotoxic at 5 M concentration, displaying strong synergism. This effect was only seen for 46a (IC50—3.3 M) albeit some other ligands had better IC50 values. Molecular modelling into the catalytic site of Tdp1 predicted plausible binding mode of 46a, effectively blocking access to the catalytic site.

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Section: Organic Synthesismentioning

confidence: 99%

The Development of Tyrosyl-DNA Phosphodiesterase 1 Inhibitors. Combination of Monoterpene and Adamantine Moieties via Amide or Thioamide Bridges

et al. 2019

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“…The obtained product was identified by comparison of the 1 H NMR and 13 C NMR spectra with those of commercially available authentic samples. All other products, 2b , 2c , 2c' , and 2c'' were identified by means of NMR spectroscopy by comparison with literature data [ 32 – 33 ].…”

Section: Methodsmentioning

confidence: 99%

Koch–Haaf reaction of adamantanols in an acid-tolerant hastelloy-made microreactor

Fukuyama¹,

Mukai²,

Ryu³

2011

Beilstein J. Org. Chem.

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SummaryThe Koch–Haaf reaction of adamantanols was successfully carried out in a microflow system at room temperature. By combining an acid-tolerant hastelloy-made micromixer, a PTFE tube, and a hastelloy-made microextraction unit, a packaged reaction-to-workup system was developed. By means of the present system, the multigram scale synthesis of 1-adamantanecarboxylic acid was achieved in ca. one hour operation.

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“…He found that both the nucleophilic and electrophilic version took place with attack syn to a remote electron-withdrawing group, and therefore anti to the better donor substituent, and to a very similar extent. 14 There is also some support for the idea that the complementary pairs would have an opposite electronic bias of the kind that we wanted to use. The transition structure for the Ireland-Claisen rearrangement is even further above the diagonal line in a More O'Ferrall-Jencks diagram than the transition structure for an unsubstituted Claisen rearrangement, 15 implying even more bond-breaking ahead of bond-making.…”

Section: Introductionmentioning

confidence: 91%

The Ireland–Claisen rearrangement as a probe for the diastereoselectivity of nucleophilic attack on a double bond adjacent to a stereogenic centre carrying a silyl group

Betson

Fleming

2003

Org. Biomol. Chem.

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The E- and Z-silyl enol ethers 4 derived from allyl 3-R-3-dimethyl(phenyl)silylpropanoate (R = Me, Pr(i) and Ph) and the Z-silyl enol ethers 7 derived from 4-R-4-dimethyl(phenyl)silylbut-2-enyl acetate (R = Me and Pr(i)) undergo Ireland-Claisen rearrangements largely in the same stereochemical sense, with C-C bond formation taking place anti to the silyl group in the conformations 22, 23 and 24 in which the hydrogen atom on the stereogenic centre is inside, more or less eclipsing the double bond. The E-silyl enol ether E-7a derived from 4-methyl-4-dimethyl(phenyl)silylbut-2-enyl acetate shows low diastereoselectivity in the alternative sense, probably because C-C bond formation takes place anti to the silyl group in the conformation 26 with the methyl group inside, but the silyl enol ether E-7b derived from 4-isopropyl-4-dimethyl(phenyl)silylbut-2-enyl acetate shows low diastereoselectivity in the normal sense. The E- and Z-silyl enol ethers 33 derived from cis-crotyl 3-phenyl-3-dimethyl(phenyl)silylpropanoate and the E-silyl enol ether 39 derived from trans-crotyl 3-phenyl-3-dimethyl(phenyl)silylpropanoate undergo Ireland-Claisen rearrangements largely in the same stereochemical sense as their allyl counterparts, but with moderately high levels of diastereocontrol in setting up the third stereogenic centre following from chair-like transition structures.

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Face Selection in Claisen Rearrangements

Cited by 22 publications

References 0 publications

The Development of Tyrosyl-DNA Phosphodiesterase 1 Inhibitors. Combination of Monoterpene and Adamantine Moieties via Amide or Thioamide Bridges

The Development of Tyrosyl-DNA Phosphodiesterase 1 Inhibitors. Combination of Monoterpene and Adamantine Moieties via Amide or Thioamide Bridges

Koch–Haaf reaction of adamantanols in an acid-tolerant hastelloy-made microreactor

The Ireland–Claisen rearrangement as a probe for the diastereoselectivity of nucleophilic attack on a double bond adjacent to a stereogenic centre carrying a silyl group

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