1,1'-(4-oxo-1-butenylene)octamethylferrocene | 158404-29-6

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 1,1'-(4-oxo-1-butenylene)octamethylferrocene
• 英文别名: (Z)-1,4-bis(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)but-3-en-1-one;iron(2+)
• CAS: 158404-29-6
• 化学式: C₂₂H₂₈FeO
• 分子量: 364.311
• InChiKey: QGULSQBUQHATCH-KVVVOXFISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.88
• 重原子数：
  24
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,1'-(4-oxo-1-butenylene)octamethylferrocene 在 NaBH₄ 作用下， 以 甲醇 、 乙醚 为溶剂， 以94%的产率得到1,1'-(4-hydroxy-1-butenylene)octamethylferrocene
  参考文献：
  名称：

  Structure, Reactivity, and Electronic Properties of [4]Ferrocenophanes and [4]Ruthenocenophanes Prepared via a Novel Heteroannular Cyclization Reaction

  摘要：

  The reactions of 1,1'-bis((trimethylsilyl)ethynyl)ferrocene and 1,1'-bis((trimethylsilyl)-ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1'-bis((trimeth-ylsilyl)ethynyl)octamethylferrocene reacted to give 1,1'-(1-methoxy-1,3-butadienylene)oc-tamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1'-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1'-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1'-(4-oxo-1-butenylene)ferrocene with alane provided 1,1'-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1'-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1'-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1'-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferro-cenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1'-(1-Methoxy-1,3-butadi-enylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) angstrom, b = 5.981(2) angstrom, c = 28.962(3) angstrom, Z = 16, and R = 0.072. 1,1'-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) angstrom, b = 9.023(2) angstrom, c = 13.940(2) angstrom, 111.296(8)-degrees, Z = 8, and R = 0.021.

  DOI：

  10.1021/om00020a026
• 作为产物：
  描述：

  1,1'-(1-methoxy-1,3-butadienylene)octamethylferrocene 在 oxalic acid 、 SiO₂ 作用下， 以 二氯甲烷 、 水 为溶剂， 以90%的产率得到1,1'-(4-oxo-1-butenylene)octamethylferrocene
  参考文献：
  名称：

  Structure, Reactivity, and Electronic Properties of [4]Ferrocenophanes and [4]Ruthenocenophanes Prepared via a Novel Heteroannular Cyclization Reaction

  摘要：

  The reactions of 1,1'-bis((trimethylsilyl)ethynyl)ferrocene and 1,1'-bis((trimethylsilyl)-ethynyl)ruthenocene with catalytic quantities of alkali-metal methoxides in methanol directly afforded the highly unsaturated [4]metallocenophanes 1,1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene, respectively, in high yields via a novel desilylation/heteroannular cyclization sequence. Analogously, 1,1'-bis((trimeth-ylsilyl)ethynyl)octamethylferrocene reacted to give 1,1'-(1-methoxy-1,3-butadienylene)oc-tamethylferrocene in high yield. The reactions of ((trimethylsilyl)ethynyl)ferrocene and ((trimethylsilyl)ethynyl)ruthenocene under identical conditions afforded ethynylferrocene and ethynylruthenocene, respectively. Synthetic elaboration of the heteroannular bridge of the cyclization products provided a route to additional [4]metallocenophanes. Treatment of 1,1'-(1-methoxy-1,3-butadienylene)ferrocene with acidic silica gel afforded 1,1'-(4-oxo-1-butenylene)ferrocene. Reaction of 1,1'-(4-oxo-1-butenylene)ferrocene with alane provided 1,1'-(1-butenylene)ferrocene, while reaction with sodium borohydride gave 1,1'-(4-hydroxy-1-butenylene)ferrocene. Dehydration of 1,1'-(4-hydroxy-1-butenylene)ferrocene on activated alumina provided 1,1'-(1,3-butadienylene)ferrocene. Similar synthetic transformations were carried out to yield the analogous series of ruthenocenophanes and octamethylferro-cenophanes. Voltammetric half-wave oxidation potentials were measured for all of the metallocenophanes in order to evaluate the electronic effect of the heteroannular bridges. X-ray crystal structure analyses were carried out on 1-1'-(1-methoxy-1,3-butadienylene)-ferrocene and 1,1'-(1-methoxy-1,3-butadienylene)ruthenocene. 1,1'-(1-Methoxy-1,3-butadi-enylene)ferrocene, C15H14FeO, crystallized in the orthorhombic space group Pcnb with a = 26.997(5) angstrom, b = 5.981(2) angstrom, c = 28.962(3) angstrom, Z = 16, and R = 0.072. 1,1'-(1-Methoxy-1,3-butadienylene)ruthenocene, C15H14RuO, crystallized in the monoclinic C2/c space group with a = 20.590(3) angstrom, b = 9.023(2) angstrom, c = 13.940(2) angstrom, 111.296(8)-degrees, Z = 8, and R = 0.021.

  DOI：

  10.1021/om00020a026

文献信息

• Control over cyclisation sequences of 1,1′-bifunctional octamethylferrocenes to ferrocenophanes
  作者：Max Roemer、Duncan A. Wild、Brian W. Skelton、Alexandre N. Sobolev、Gareth L. Nealon、Matthew J. Piggott、George A. Koutsantonis

  DOI：10.1039/c7dt02037f

  日期：——

  This paper describes the facile synthesis of a number of electron rich octamethyl[1.4]ferrocenophanes with unsaturated handles from 1,1′-bis(1-chlorovinyl)octamethylferrocene. Treatment of this reactive compound with sodium hydroxide in DMF initiates a series of reactions resulting in the formation of four different ferrocenophanes. The most complex of these products arises from a cascade of cyclisations

  本文描述了从1,1'-双（1-氯乙烯基）八甲基二茂铁轻松合成具有不饱和手柄的许多富电子八甲基[1.4]二茂铁杂环烯。在DMF中用氢氧化钠处理这种反应性化合物会引发一系列反应，从而导致形成四个不同的二茂铁基铁烷。这些产品中最复杂的是来自一系列环化反应，产生了具有中心稠合环丁烯的不寻常，不对称的双二茂铁碳烷。通过控制NaOH的浓度可以控制反应的结果。提出了机制，并得到了DFT计算的支持。