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.

我们使用我们最初的方法进行了新的七-2,4,6-三烯醛的合成，该方法基于使用β-烷氧基烯基锂的Wittig型烯化反应，其简单过程如下所示。第一个是β-烷氧基烯基锂与醛和酮的亲电加成，第二个是烯丙醇的水解。醛和酮的α-硫基-、α-硒基和α-氰基甲酰化串联甲酰化得到光敏2,4,6-三(苯基硫基)-,4-氰基-2,6-双(苯基硫基)。 -和6-氰基-2,4-双(苯基-硫基)七-2,4,6-三烯醛分别进行新的串联环化，得到2-氧杂-或2-氮杂-双环。 [3.3.0]八-3,7-二烯，同时，β-全氟烷基-β-烷氧基烯基锂。醛和连续水合得到α,β-不饱和全氟烷基酮，这是制备含氟生物活性化合物的新前体，然而，串联全氟酰化得到4,6-双(全氟烷基)-2H-吡喃，而不是。 2,4-二烯基酮 综上所述，我们介绍了几种 2,4,6-七烯醛。发现这里制备的化合物具有高度光敏性，可产生新的双环化合物。特别是，2-氰基庚三烯醛的制备导致直接形成氧杂双环化合物，而不是三烯醛。

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 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, 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, 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