• Title/Summary/Keyword: Ketones.

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Medium effects on the H-Atom Abstraction and Silyl-Transfer Photoreactions of Silylalkyl Ketones

  • Oh, Sun-Wha
    • Journal of Photoscience
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    • v.12 no.1
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    • pp.47-50
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    • 2005
  • Mediumeffects have been explored on the competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl-substituted phenyl ketones. The chemical selectivities of photochemical reactions of silylalkyl phenyl ketones appear to depend on medium polarity, medium silophilicity, added metal cation and alkyl length. Irradiations of silylalkylketones in aqueous solvent system and in presence of metal cation such as $Li^+$ and $Mg^{+2} $lead to formation of acetophenone predominantly by the sequential SET-silyl transfer route.

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Reaction of Lithium 2-Pyridyloxyalkylcuprates Having Improved Thermal Stability with Acid Chlorides and $\alpha,\beta$-Unsaturated Ketones

  • Lee, Phil-Ho;Shim, Sang-Chul;Kim, Sung-Gak
    • Bulletin of the Korean Chemical Society
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    • v.7 no.6
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    • pp.425-428
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    • 1986
  • A new heterocuprate containing 2-pyridyloxy ligand, lithium 2-pyridyloxy-n-butylcuprate, has shown improved thermal stability and it reacts with acid chlorides to afford the corresponding ketones in high yields. Similarly, it can be effectively utilized in conjugate addition reactions of $\alpha,\beta$-unsaturated ketones. Of synthetic significance is that the complete utilization of n-butyl group in lithium 2-pyridyloxy-n-butylcuprate has been observed.

Viologen-mediated Reductive Transformations of gem-Bromonitro Compounds and $\alpha$-Nitro Ketones by Sodium Dithionite

  • Kwanghee Koh Park;Won Kyou Joung;Sook Young Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.461-465
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    • 1993
  • Reductive transformations of gem-bromonitro compounds and ${\alpha}$-nitro ketones were carried out conveniently with sodium dithionite by using dioctyl viologen as an electron-transfer catalyst in dichloromethane-water two-phase system:the bromine atom in gem-bromonitro compounds and the nitro group in ${\alpha}$-nitro ketones are replaced by hydrogen.

A Practical Synthesis of Morita-Baylis-Hillman Adducts of Aryl Vinyl Ketones Catalyzed by a Proton Donor

  • Kim, Sung-Hwan;Kim, Se-Hee;Lim, Cheol-Hee;Kim, Jae-Nyoung
    • Bulletin of the Korean Chemical Society
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    • v.33 no.6
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    • pp.2023-2027
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    • 2012
  • An efficient and practical synthesis of MBH adducts of aryl vinyl ketones was developed using DABCO and 4-nitrophenol as a proton donor. Addition of a proton donor and the use of excess amounts (3.0 equiv) of aldehydes were highly beneficial for the yields of MBH adducts of aryl vinyl ketones.

Selective Reduction of Carbonyl Compounds with Dilsobutyldialkylaminoalanes

  • 차진순;권상용;권오운;김종미;송한철
    • Bulletin of the Korean Chemical Society
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    • v.17 no.10
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    • pp.900-905
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    • 1996
  • Details are described of reaction of carbonyl compounds with diisobutyldialkylaminoalane (DIBAL-NR2; R=Et, i-Bu, Ph) in order to establish their reduction characteristics. The reagents were extremely mild and reduced only aldehydes and ketones effectively in ethyl ether at 25 ℃. The stereoselectivity in the reduction of representative cyclic ketones appeared not so high but quite different from that obtained by DIBAL-H itself. The reagents reduced α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols without any detectable 1,4-reduction products. DIBAL-NR2 also achieved the selective reduction of aldehydes or ketones in the presence of keto or other readily reducible functional group, however the chemoselectivity was less satisfactory than that achieved by diisobutylethoxyalane (DI-BAL-OEt).

Kinetics and Mechanism of Oxidation of Styryl Biphenyl and Styryl Fluorenyl Ketones by Pyridinium Chlorochromate

  • 성대동;P. Ananthakrishna Nadar
    • Bulletin of the Korean Chemical Society
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    • v.20 no.12
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    • pp.1487-1492
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    • 1999
  • The kinetics of oxidation of substituted styryl 4-biphenyl ketones and of substituted styryl 2-fluorenyl ketones by pyridinium chlorochromate (PCC) have been studied in 90% acetic acid- 10% water (v/v) containing perchloric acid and NaClO₄ at $10^0,\;20^0,\;30^0$ and 40℃. The reactions are first order in styryl ketones and PCC. The second order rate constants are well correlated only with σ$^+$ constants implying development of positive charge adjacent to benzene ring in the transition state. The effects of varying [HClO₄] and the percentage of acetic acid on the reactions have also been analysed. A mechanism involving nucleophilic attack of PCC leading to an unsymmetric intermediate from which epoxides are formed is proposed.

Selective Reduction of Carbonyl Compounds with Al-Alkoxydiisobutylalanes

  • 차진순;권오운;김종미;전중현;이영수;이형수;조성동
    • Bulletin of the Korean Chemical Society
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    • v.19 no.2
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    • pp.236-242
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    • 1998
  • Reaction of carbonyl compounds with Al-alkoxydiisobutylalane (DIBAOR, R=H, Et, i-Pr, t-Bu) has been investigated in detail so as to establish their usefulness as selective reducing agents in organic synthesis. The reagents appear to be extremely mild and can reduce only aldehydes and ketones effectively under mild conditions. All the other common organic functional groups are not affected by these reagents. The reagents can also reduce α,β-unsaturated aldehydes and ketones to the corresponding allylic alcohols without any detectable 1,4-reduction. Furthermore, the reagents show a highly chemoselective discrimination between aldehyde and ketone, between aldehydes, and between ketones. Even more remarkable is the stereoselective reduction of cyclic ketones to the thermodynamically more stable alcohol epimers.