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Synthesis of Helicenes and Related Compounds Based on the Domino Cationic Cyclization of gem- Difluoroalkenes

Synthesis of Helicenes and Related Compounds Based on the Domino Cationic Cyclization of gem- Difluoroalkenes
基于偕二氟烯烃多米诺阳离子环化的螺烯及相关化合物的合成
批准号:
17550031
负责人:
ICHIKAWA Junji
金额:
$2.37万
依托单位:
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (C)
财政年份:
2005
资助国家:
日本
项目状态:
已结题
起止时间:
2005 至 2006

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中文摘要
翻译
荧光素占有(1) α-碳稳定性效应由其未共享的电子对捐赠给α-碳的真空p-轨道,(2)其离开组能力作为一种氟离子(F^-),导致其高电性。我们已经完成了一个熔化的多分子化合物的合成,从宝石-异氟烯烃开始。(1,1-difluoro-1-alkenes)通过两种属性中的两种反应都完全可用,1,1-difluoro-1-alkenes在C-3、4或5个位置被处理为FSO_3H·SbF_5通过α-氟ocarbocation进行未经验证的弗里德里克工艺循环化,由C-F键的自发水合作用形成,包括五个、六个或七个成员环,上面有动力的循环中的关键步骤是弗里德尔-工艺品类型反应,在哪里需要使用魔力酸来激活异氟烯烃的动力。为了避免这种强烈的酸性条件,我们已经成功地通过过渡约会来进行这种类型的循环化 ... More al complexes,如cationic Pd, Ru和Au complexes。特别是, [Pd(MeCN)_4](BF_4)_2有效地推广了循环化来给予多环化合物产品。关于用Magic Acid和difluorolokenes携带两个芳基组通过成功地产生了两种α-氟酸化合物的显性循环化,其中一个被内分子芳基组捕获成两个6成员的戒指。循环化的产品已经完全被脱氢化,可以被腐蚀成腐蚀性的螺旋体。使用这一策略,我们已经完成了[4]到[6]的合成,仅在三个步骤中可以从容易获得的化合物:(一)1,1-difluoro-1-alkenes的准备, (二)多米诺弗里德尔工艺品类型循环,和(iii)脱氢化.用Et_2 AlCl诱导的Friedel-Crafts-承载2-三氟甲基-1-烯烃组的治疗类型循环化通过对碳γ组的攻击对荧光素给予外二氟甲基替代的环化合物,以及对螺旋前cursor的攻击。Less(低)
英文摘要
Fluorine possesses (1) α-carbocation stabilizing effect caused by donation of its unshared electron pair to the vacant p-orbital of the α-carbon, despite (2) its leaving group ability as a fluoride ion (F^-) due to its high electronegativity. We have accomplished the synthesis of fused polyaromatic compounds starting from gem-difluoroalkenes (1,1-difluoro-1-alkenes) via the reactions where both of the two properties were fully utilized.1,1-Difluoro-1-alkenes bearing a phenyl group at the C-3, 4, or 5 position were treated with FSO_3H・SbF_5 to undergo Friedel-Crafts cyclization via α-fluorocarbocations, followed by spontaneous hydrolysis of the C-F bond to afford bicyclic ketones including a five, six, or seven-membered ring.The key step in the above mentioned cyclization was the Friedel-Crafts-type reaction, where Magic acid was required to activate the difluoroalkene moiety. To avoid such strong acidic conditions, we have succeeded to conduct this type of cyclization by transition met … More al complexes, such as cationic Pd, Ru, and Au complexes. Especially, [Pd(MeCN)_4](BF_4)_2 effectively promoted the cyclization to give polycyclic products.On treatment with Magic acid, the difluoroalkenes bearing two aryl groups underwent the domino cyclization via successively generated two kinds of α-fluorocarbocations, which were trapped by the intramolecular aryl groups to construct two 6-membered rings. The cyclized products were readily dehydrogenated to afford substituted helicenes. Using this strategy we have accomplished the syntheses of [4] to [6]helicenes from easily available compounds in only three steps: (i) the preparation of 1,1-difluoro-1-alkenes, (ii) the domino Friedel-Crafts-type cyclization, and (iii) dehydrogenation.Treatment of 2-trifluoromethyl-1-alkenes bearing an aryl group with Et_2AlCl induced Friedel-Crafts-type cyclization via attack of the aryl group on the carbon γ to the fluorine to give exo-difluoromethylene-substituted cyclic compounds, the helicene precursors. Less
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Friedel-Crafts Cyclization of 1,1-Difluoro-1-alkenes : Synthesis of Benzene-Fused Cyclic Ketones via α-Fluorocarbocations
1,1-二氟-1-烯烃的傅克环化:通过 α-氟碳正离子合成苯稠环酮
DOI: --
发表时间: 2005
期刊: Synthesis 2005
影响因子: --
作者: [J.Ichikawa, H.Jyono, T.Kudo, M.Fujiwara, M.Yokota]
通讯作者: M.Yokota
DOI: 10.1021/ol060912r
发表时间: 2006-07-20
期刊: ORGANIC LETTERS
影响因子: 5.2
作者: [Ichikawa, Junji, Kaneko, Mikio, Yokoyama, Takaharu]
通讯作者: Yokoyama, Takaharu
Fiedel-Crafts-Type Cycliations
Fiedel-Crafts 型循环
DOI: --
发表时间: 2006
期刊: Organic Letters 8
影响因子: --
作者: [J.Ichikawa, M.Kaneko, M.Yokota, M.Itonaga, T.Yokoyama]
通讯作者: T.Yokoyama
Friedel- Crafts Cyclization of 1,1-Difluoro-1-alkenes : Synthesis of Benzene-Fused Cyclic Ketones via a-Fluorocarbocations.
1,1-二氟-1-烯烃的弗里德尔-克拉夫茨环化:通过α-氟碳正离子合成苯稠环酮。
DOI: --
发表时间: 2005
期刊: Synthesis 2005
影响因子: --
作者: [J.Ichikawa, H.Jyono, T.Kudo, M.Fujiwara, M.Yokota]
通讯作者: M.Yokota
Catalytic Syntheses of Fluorine-Containing Compounds via Fluorine-Substituted Transition Metal Carbene Complexes
  • 批准号:
    16K13943
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
  • 资助金额:
    $2.33万
  • 财政年份:
    2016
  • 负责人:
    ICHIKAWA Junji
  • 依托单位:
Electrophilic activation and reactivity control of fluorinated alkenes by transition-metal complexes
  • 批准号:
    23655028
  • 项目类别:
    Grant-in-Aid for Challenging Exploratory Research
  • 资助金额:
    $2.5万
  • 财政年份:
    2011
  • 负责人:
    ICHIKAWA Junji
  • 依托单位:
A GENERAL METHOD FOR THE SYNTHESIS OF POLYCYCLIC AROMATIC HYDROCARBONS BASED ON SEQUENCIAL CATIONIC CYCLIZATIONS
Construction of Fused Polycyclic System via Tandem Cationic Cyclization by Using the Properties of Fluorine
  • 批准号:
    14540488
  • 项目类别:
    Grant-in-Aid for Scientific Research (C)
  • 资助金额:
    $2.3万
  • 财政年份:
    2002
  • 负责人:
    ICHIKAWA Junji
  • 依托单位:
海外基金