A New Polyene Analog : Its Preparation and Photo-Reaction

一种新的多烯类似物：其制备和光反应

• 批准号: 12672052
• 负责人: YOSHIMATSU Mitsuhiro
• 金额: $ 2.18万
• 依托单位: Gifu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12672052/
• 关键词: β-alkoxyalkenyl lithium; hepta-2,4,6-trienal; polyene; α,β-unsaturated ketone; perfluoroalkyl; vinyl sulfide; vinyl selenide; formylation; α,β-unsaturated ketone; vinyl selenide; トリエナール; ポリエン; ペルフルオロアルキル; オレフィン化; ピラン

We have performed the syntheses of the new hepta-2,4,6-trienals using our original methodology, which was based on the Wittig type olefinations using β-alkoxyalkenyl lithiums. A simple process has been shown as follows. It contains two steps, a first is a electrophilic addition of the β-alkoxyalkenyl lithium with aldehydes and ketones, a second is a hydrolysis of the allylic alcohols. We have succeeded the α-sulfenyl-, α-selenenyl and α-cyano formylation of aldehydes and ketones. The tandem formylation gave the photo-sensitive 2,4,6-tris(phenylsulfenyl)-, 4-cyano-2,6-bis(phenylsulfenyl)- and 6-cyano-2,4-bis(phenyl-sulfenyl)hepta-2,4,6-trienals, respectively. Photo-reactions of these trienals underwent the new tandem cyclization to afford the 2-oxa- or 2-aza-bicyclo[3.3.0]octa-3,7-dienes. While, the β-perfluoroalkyl-β-alkoxyalkenyl lithiums with aldehydes and the successive hydrations afforded α,β-unsaturated perfluoroalkyl ketones, which were the novel precursors in the preparations of the fluorine-containing bioactive compounds. However, tandem perfluoroacylations gave the 4,6-bis(perfluoroalkyl)-2H-pyrans, not the 2,4-dienyl ketones. In summary, the several kinds of 2,4,6-heptatrienals we prepared here, are found to be highly-photo-sensitive to give the new bicyclic compounds. In particular, the preparation of the 2-cyanoheptatrienal lead to the direct formation of the oxabicyclic compounds, not the trienals.

我们已经使用我们的原始方法进行了新的Hepta-2,4,6-三体的合成，该方法基于使用β-烷氧基烯基锂的Wittig型烯烃。一个简单的过程如下所示。它包含两个步骤，第一个是用醛和酮的β-烷氧基烯基锂的亲电性添加，第二个是对烯丙基醇的水解。我们已经成功使用了醛和酮的α-磺苯基，α-苯基和α-甲氧配方。串联配方给出了光敏感的2,4,6-Tris（苯基磺酰基） - ，4-甲基-2,6-双基（苯基磺酰基） - 和6-甲基-2,4-双（苯基甲基苯基）HEPTA-2,4,4,6-6-4-4,6-6-6-6-6-6-6-6-6-6-6-6-6-6-二烯。在新的串联自行车下进行这些三角体的照片反应，以提供2-oxa-或2-aza-bicyclo [3.3.0]八八元素。同时，带有醛的β-全氟烷基-β-烷氧基烯基锂和成功的水合提供了α，β-β-不饱和的完美素烷基酮，这是富含荧光纤维含量的生物活性化合物制备的新型前体。然而，串联全氟烷基-2H-Pyrans，而不是2,4-二烯基酮。总而言之，我们在这里制备的几种2,4,6-氢蛋白酶具有高度敏感性，可以提供新的生物化合物。特别是，2-苯二甲酰胺的制备导致草oxabiclic化合物的直接形成，而不是三角形。

项目成果

Y.Matsubara and M.Yoshimatsu: "A Novel ・ -Seleno- or Nonselenoperfluoroacyl Olefination of Aldehydes and Ketones Using ・ -Ethoxy- ・ -perfluoroalkyl Vinylic Selenides"J.Org.Chem.. 65. 4456-4459 (2000)

Y.Matsubara 和 M.Yoshimatsu：“使用 ・-乙氧基- ・-全氟烷基乙烯基硒化物对醛和酮进行新颖的 ・-硒代-或非硒代全氟酰基烯化”J.Org.Chem.. 65. 4456-4459 (2000)

M.Yoshimatsu, S.Kinoshita: "Direct Lithiation and Alkylation of Trifluoromethyl Enol Ethers Having a β-Sulfur Substituent"Chem. Pharm. Bull.. 48. 145-147 (2000)

M.Yoshimatsu, S.Kinoshita：“具有 β-硫取代基的三氟甲基烯醇醚的直接锂化和烷基化”，Chem. Bull. 48. 145-147 (2000)

M.Yoshimatsu and M.Hibino: "First Synthesis of a ・ -Trifluoromethyl Allenol Ether via the Julia-Lythgoe Process"Chem.Pharm.Bull.. 48. 1395-1398 (2000)

M.Yoshimatsu 和 M.Hibino：“通过 Julia-Lythgoe 工艺首次合成 α-三氟甲基二烯醇醚”Chem.Pharm.Bull.. 48. 1395-1398 (2000)

M.Yoshimatsu, M.Kuribayashi: "A Novel Sc(OTf')_3-Catalyzed Prop-2-ynylation and Penta-2,4-diynylation of Soft Nucleophiles"Synlett. 1799-1801 (2001)

M.Yoshimatsu、M.Kuribayashi：“新型 Sc(OTf)_3-催化软亲核试剂的 Prop-2-ynyllation 和 Penta-2,4-diynyllation”Synlett。

M.Yoshimatsu, S.Yamaguchi, Y.Matsubara: "A General α-Cyanoformylation Using α-Lithio-β-ethoxyacrylonitrile : Application to the syntheses of New 6-Cyano-2,4-bis(phenylthio)-and 4-Cyano-2,6-bis(phenylthio)hepta-2,4,6-trienals"J. Chem. Soc., Perkin Trans. 1

M. Yoshimatsu、S. Yamaguchi、Y. Matsubara：“使用 α-锂-β-乙氧基丙烯腈的一般 α-氰基甲酰化：在新 6-氰基-2,4-双（苯硫基）-和 4-氰基合成中的应用-2,6-双(苯硫基)七-2,4,6-三烯醛”J. Chem. Soc., Perkin Trans. 1