Reaction of organotitanium species prepared from gem-dihalides and titanocene(II)

偕二卤化物与二茂钛(II)制备有机钛的反应

基本信息

  • 批准号:
    10640573
  • 负责人:
  • 金额:
    $ 0.58万
  • 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:
    1998
  • 资助国家:
    日本
  • 起止时间:
    1998 至 1999
  • 项目状态:
    已结题

项目摘要

Development of the new synthetic reactions utilizing organotitanium reagents prepared by the reaction of gem-dihalides with titanocene(II) species were studied. The carbonyl olefination using a gem-Dichloride-CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 System, transformation of ketones into 1-chloro and 1,1-dichloro-1-alkenes, and titanocene(II)-promoted cyclization of gem-dihalides having a terminal olefin moiety were examined and following results were obtained.1. Synthesis of tetrasubstituted olefins by the titanocene(II)-promoted olefination of carbonyl compounds using gem-dichlorides .... The organotitanium species prepared from gem-dichlorides and CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 reacted with ketones and carboxylic esters to afford tetrasubstituted olefins and trisubstituted enol ethers in good yields, respectively.2. Synthesis of 1-chloro and 1,1-dichloro-1-alkenes .... The reaction of the organotitanium species prepared from carbon tetrachloride with ketones produced the 1,1-dichloro-1-alkenes in good yields. The similar olefination of ketones using chloroform afforded the 1-chloro-1-alkenes and 1,1-dichloro-1-alkenes, the ratio of which refracted the steric demand on the ketones.3. Titanocene(II)-promoted cyclization of gem-dihalides having a terminal olefin moiety .... The bicyclo[n.1.0] derivatives were produced by the simple treatment of the gem-dihalides having a terminal olefin moiety with CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 in good yields. This result suggested that the organotitanium species generated by the reaction of gem-dihalide with CpィイD22ィエD2Ti[P(OEt)ィイD23ィエD23]ィイD22ィエD2 was different from the one prepared from thioacetal. This cyclization may proceed through gem-dititanium species.
研究了利用二卤化宝石与二茂钛(II)反应制备的有机钛试剂的新合成反应。羰基烯化作用使用gem-Dichloride-CpィイD22摊位ィエD2Ti [P(诗人)ィイc15ィエc15]ィイD22摊位ィエD2系统,酮类转换为1-chloro, 1-dichloro-1-alkenes, titanocene (II)提升环合的gem-dihalides终端烯烃,检测后一部分结果obtained.1。二氯宝石催化二茂钛烯烃羰基烯烃合成四取代烯烃....由宝石二氯化物和Cp γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ γ。1-氯和1,1-二氯-1烯烃的合成....以四氯化碳为原料制备的有机钛与酮反应,产率较高,可制得1,1-二氯-1-烯烃。用氯仿对酮类进行类似的烯烃反应,得到1-氯-1-烯烃和1,1-二氯-1-烯烃,其比例反映了对酮类的立体需求。二茂钛(II)促进了具有末端烯烃部分的宝石二卤化物的环化....bicyclo [n.1.0]衍生品是由简单的治疗gem-dihalides与Cp末端烯烃基ィイD22摊位ィエD2Ti [P(诗人)ィイc15ィエc15]ィイD22摊位ィエD2收益良好。结果表明,由二卤化宝石与Cp (P(OEt))反应生成的有机钛与由硫缩醛制备的有机钛不同。这种环化可以通过宝石-双钛物种进行。

项目成果

期刊论文数量(6)
专著数量(0)
科研奖励数量(0)
会议论文数量(0)
专利数量(0)
Tooru Fujiwara: "Transformation of Ketones into Chloro and 1,1-Dichloro-1-alkenes by Means of a Polychloromethane-Titanocene(II) system"Tetrahedeon. 55. 2475-2486 (1999)
Toru Fujiwara:“通过多氯甲烷-二茂钛 (II) 系统将酮转化为氯和 1,1-二氯-1-烯烃”Tetrahedeon。
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Tooru Fujiwara: "Carbonyl olefination by Means of a gem-Dichloride-CpィイD22ィエD2Ti[P(Oet)ィイD23ィエD2]ィイD22ィエD2 System"J. Org. Chem.. 63. 7286-7288 (1998)
Toru Fujiwara:“通过宝石-二氯化物-CpD22Ti[P(Oet)D23D2]D22D2 系统进行羰基烯化”J. Org. 63. 7286-7288 (1998)
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    0
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藤原 徹: "Carbonyl Olefination by Means of a gem-Dichloride-Cp_2Ti[P(OEt)_3]_2 System" J.Org.Chem.63・21. 7286-7288 (1998)
藤原彻:“通过宝石-二氯化物-Cp_2Ti[P(OEt)_3]_2 系统进行羰基烯化”J.Org.Chem.63・21 (1998)。
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藤原 徹: "Carbonyl Olefination by Means of a gem-Dichloride-C_<p2> Ti[P(Oet)_3]_2 System"J. Org. Chem.. 63. 7286-7288 (1998)
Toru Fujiwara:“通过宝石-二氯化物-C_<p2> Ti[P(Oet)_3]_2 系统进行羰基烯化”J. 63. 7286-7288 (1998)
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藤原 徹: "Transformation of Ketones into 1-chloro and 1.1-Dichloro-1-alkenes by Means of a Polychloromethane-Titanocene(II) System"Tetrahedron. 55. 2475-2486 (1999)
Toru Fujiwara:“通过多氯甲烷-二茂钛 (II) 系统将酮转化为 1-氯和 1,1-二氯-1-烯烃”四面体 55。2475-2486 (1999)
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