(E,E/E,Z)-[1-iodo-4-ferrocenyl-1,3-diene] | 263568-69-0

• 英文名称: (E,E/E,Z)-[1-iodo-4-ferrocenyl-1,3-diene]
• CAS: 263568-69-0；910911-62-5
• 化学式: C₁₄H₁₃FeI
• 分子量: 364.009
• InChiKey: MNSPRQIURAQUFR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
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• 可旋转键数：
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• 环数：
  None
• sp3杂化的碳原子比例：
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• 拓扑面积：
  None
• 氢给体数：
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• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-硝基苯乙烯 、 (E,E/E,Z)-[1-iodo-4-ferrocenyl-1,3-diene] 在 palladium acetate 、 tri(4-tolyl)arsine 、 lithium chloride 作用下， 以 乙腈 为溶剂， 以55%的产率得到
  参考文献：
  名称：

  Novel Catalytic Hunsdiecker−Heck (CHH) Strategy toward All-E Stereocontrolled Ferrocene-Capped Conjugated Push−Pull Polyenes

  摘要：

  Halodecarboxylation reaction of ferrocenylacrylic acid 1 and ferrocenyldienoic acid 3d with N-bromo- and N-iodosuccinimide in the presence of catalytic tetrabutylammonium trifluoroacetate at -40 degrees C and -78 degrees C affords the corresponding beta-halovinylferrocenes 2a, 2b and delta-haloferrocenyldiene 4 in 37-72% yields. Heck reaction of beta-iodovinylferrocene 2a with vinyl substrates (CH2=CH-Z where Z = CO2Me, CO2Et, COMe, CO2H, CONH2, 4'-NO2C6H4) in the presence of tri(4-tolyl)arsine/palladium acetate/lithium chloride/triethylamine in acetonitrile at 35-80 degrees C affords the corresponding ferrocenyldienes 3a-3f in 50-81% isolated yields. Similar reaction of delta-iodoferrocenyldiene 4 with vinyl substrates (CH2=CH-Z where Z = CO2Me, CO2Et, CO2H, 4'-NO2C6H4) affords the corresponding ferrocenyltrienes 5a-5d in 55-87% isolated yields. The ferrocene-capped conjugated dienes and trienes show excellent all-E stereoselectivity (vide NMR). The electronic, redox, and nonlinear optical properties of ferrocenylpolyenes have been evaluated. The data suggest that upon increasing the polyene chain length, (a) the absorption maxima shifts progressively to higher wavelength, (b) the oxidation potential of the Fc/Fc(+) couple (E-1/2) decreases, and (c) the HRS-derived second-order NLO response (beta) increases. From the insights derived from semiempirical calculation (ZINDO/1), a mechanism for the halodecarboxylation reaction has been proposed suggesting the prior formation of tetrabutylammonium salt of ferrocenylacrylic acid I. Attack of the halogenium atom at the pi(c=c) in I leads to the formation of intermediate II, and the latter triggers the elimination of carbon dioxide.

  DOI：

  10.1021/om000020+
• 作为产物：
  描述：

  N-碘代丁二酰亚胺 、 (E,E)-[5-ferrocenyl-2,4-pentadienoic acid] 在 tetrabutylammonium trifluoroacetate 作用下， 以 二氯甲烷 为溶剂， 以37%的产率得到(E,E/E,Z)-[1-iodo-4-ferrocenyl-1,3-diene]
  参考文献：
  名称：

  Novel Catalytic Hunsdiecker−Heck (CHH) Strategy toward All-E Stereocontrolled Ferrocene-Capped Conjugated Push−Pull Polyenes

  摘要：

  Halodecarboxylation reaction of ferrocenylacrylic acid 1 and ferrocenyldienoic acid 3d with N-bromo- and N-iodosuccinimide in the presence of catalytic tetrabutylammonium trifluoroacetate at -40 degrees C and -78 degrees C affords the corresponding beta-halovinylferrocenes 2a, 2b and delta-haloferrocenyldiene 4 in 37-72% yields. Heck reaction of beta-iodovinylferrocene 2a with vinyl substrates (CH2=CH-Z where Z = CO2Me, CO2Et, COMe, CO2H, CONH2, 4'-NO2C6H4) in the presence of tri(4-tolyl)arsine/palladium acetate/lithium chloride/triethylamine in acetonitrile at 35-80 degrees C affords the corresponding ferrocenyldienes 3a-3f in 50-81% isolated yields. Similar reaction of delta-iodoferrocenyldiene 4 with vinyl substrates (CH2=CH-Z where Z = CO2Me, CO2Et, CO2H, 4'-NO2C6H4) affords the corresponding ferrocenyltrienes 5a-5d in 55-87% isolated yields. The ferrocene-capped conjugated dienes and trienes show excellent all-E stereoselectivity (vide NMR). The electronic, redox, and nonlinear optical properties of ferrocenylpolyenes have been evaluated. The data suggest that upon increasing the polyene chain length, (a) the absorption maxima shifts progressively to higher wavelength, (b) the oxidation potential of the Fc/Fc(+) couple (E-1/2) decreases, and (c) the HRS-derived second-order NLO response (beta) increases. From the insights derived from semiempirical calculation (ZINDO/1), a mechanism for the halodecarboxylation reaction has been proposed suggesting the prior formation of tetrabutylammonium salt of ferrocenylacrylic acid I. Attack of the halogenium atom at the pi(c=c) in I leads to the formation of intermediate II, and the latter triggers the elimination of carbon dioxide.

  DOI：

  10.1021/om000020+