• Title/Summary/Keyword: $\alpha,\beta$-Unsaturated carbonyl compounds

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Reductive Amination of ${\alpha}$,${\beta}$-Unsaturated Carbonyl Compounds with Tetracarbonylhydridoferrate as a Reducing Agent (${\alpha}$,${\beta}$-不飽和 카르보닐化合物의 還元 아미노화反應)

  • Kim Hong-Seok;Shim Sang Chul;Shim Sang Chull
    • Journal of the Korean Chemical Society
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    • v.23 no.2
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    • pp.99-103
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    • 1979

  • The reductive amination of three ${\alpha}$,${\beta}$-unsaturated aldehydes, cinnamaldehyde, crotonaldehyde, and acrolein are carried out successfully by tetracarbonylhydridoferrate in the presence of various primary amines. In a typical reaction, a mixture of potassium tetracarbonylhydridoferrate (22 mmole), an amine (22∼44 mole) and ${\alpha}$,${\beta}$-unsaturated aldehyde (22 mmole), in ethanol (30∼50 ml) was stirred for 9∼60 hours at room temperature under carbon monoxide atmosphere. All the products were characterized as secondary amines by mass, infrared, and nmr spectra as well as gas chromatographic data.

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Wet SiO2 As a Suitable Media for Fast and Efficient Reduction of Carbonyl Compounds with NaBH3CN under Solvent-Free and Acid-Free Conditions

  • Kouhkan, Mehri;Zeynizadeh, Behzad
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2961-2966
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    • 2010

  • Reduction of carbonyl compounds such as aldehydes, ketones, $\alpha,\beta$-unsaturated enals and enones, $\alpha$-diketones and acyloins was carried out readily with $NaBH_3CN$ in the presence of wet $SiO_2$ as a neutral media. The reactions were performed at solvent-free conditions in oil bath (70 - $80^{\circ}C$) or under microwave irradiation (240 W) to give the product alcohols in high to excellent yields. Regioselective 1,2-reduction of conjugated carbonyl compounds took place in a perfect selectivity without any side product formation.

  • https://doi.org/10.5012/bkcs.2010.31.10.2961 인용 PDF KSCI

Selective Epoxidation and Reduction of Rigid Cyclic ${\alpha},{\beta}$-Unsaturated Carbonyl Compounds (환상 ${\alpha},{\beta}$-불포화 카르보닐 화합물의 선택적 에폭시화 및 환원)

  • Ma, Eun-Sook
    • YAKHAK HOEJI
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    • v.49 no.6
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    • pp.443-448
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    • 2005

  • Diosgenin (25 (R) - spirost-5-en-3$\beta$ -ol) was oxidized with 2,3-dichloro -5,6-dicyano-1,4-benzoquinone to form 25(R)-1,4,6-spirostatrien-3-one (1) as rigid cyclic $\alpha$,$\beta$-unsaturated carbonyl compound. This compound was reacted with $H_{2}O_{2}$, m-chloroperoxybenzoic acid (mCPBA), NaOCl in the presence with (R,R)- or (S,S)-Jacobsen catalyst, tert-butyl-hydroperoxide (TBHP) in Mo$(CO)_{6}$, and in VO $(acac)_{2}$ catalyst, respectively, 25(R) -1,4,6-spirostatrien -3-one (1) was reduced with $NaBH_{4}$ L-Selectride, $LiAIH_{4}$,$BH_{3}$ $\cdot$$(CH_{3})_{2}S$, Superhydride, Red-Al, and lithium tri-tert-butoxyaluminium hydride. And 25(R)-4,6-spirostadien-3$\beta$-ol (4) was treated with $H_{2}O_{2}$, mCPBA, TBHP in D - (-) - and L-(+)-diisopropyltar-trate and $Ti(OiPr)_{4}$ condition (Sharpless asymmetric epoxidation), TBHP in $Mo(CO)_{6}$, and in $VO(acac)_{2}$ catalyst, respectively.

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A New Synthesis of Triphenylphosphorane Ylide Precursors to α-Keto Amide/Ester and Tricarbonyl Units via Horner-Wadsworth-Emmons Reaction

  • Lee, Kie-Seung
    • Bulletin of the Korean Chemical Society
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    • v.31 no.10
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    • pp.2776-2782
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    • 2010

  • Newly developed Horner-Wadsworth-Emmons (HWE) reagents 5 having triphenylphosphorane ylide subunits readily condensed with various carbonyl compounds under mild reaction conditions to afford $\beta,\gamma$-unsaturated $\alpha$-keto triphenylphorane ylides in good to excellent yields, which were hydrogenated over Pd-C (10%)/$H_2$ (1 atm) to give the corresponding $\alpha$-keto triphenylphorane ylides in quasi-quantitative yields. These triphenyphosphorane ylides have been utilized as the precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units in Wasserman's synthetic protocols, and have previously been prepared only from carboxylic acids/acid chlorides. Our new approaches provide excellent alternatives for the synthesis of triphenylphosphorane ylide precursors to $\alpha$-keto amide/ester and vicinal tricarbonyl units directly from carbonyl compounds in good to excellent yields.

  • https://doi.org/10.5012/bkcs.2010.31.10.2776 인용 PDF KSCI

Selective Reduction of Organic Compounds with Non-Free Hydride Reducing Agents

  • Cha, Jin Soon
    • Journal of Integrative Natural Science
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    • v.1 no.3
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    • pp.192-194
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    • 2008

  • A series of non-free hydride reducing systems containing boron or aluminum atom, which possess no metal-hydride bond but an available hydrogen at a branched ${\beta}$-position, has been applied to the selective reduction (chemo--, regio-, and stereoselective reduction) of organic compounds. The systems, comprised of diisopinocampheylborane and diisobutylalane derivatives, exhibited almost perfect selectivities in the reduction of aldehydes and ketones. The characteristics features of this systems leading to a perfect transformation have been depicted in this report, especially in the 1) Reduction of ${\alpha}$,${\beta}$-Unsaturated Carbonyl Compounds to Allylic Alcohols via 1,2-Reduction, 2) Chemoselective Reduction between Structurally Different Carbonyl Compounds, and 3) Stereoselective Reduction of Cyclic Ketones.

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