(E)-(5-iodopent-1-enyl)benzene | 910788-16-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-(5-iodopent-1-enyl)benzene
• 英文别名: (E)-(5-iodopent-1-en-1-yl)benzene；[(E)-5-iodopent-1-enyl]benzene
• CAS: 910788-16-8
• 化学式: C₁₁H₁₃I
• 分子量: 272.129
• InChiKey: AFWOTRIOOOBRJJ-WEVVVXLNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (E)-(5-iodopent-1-enyl)benzene 在 草酰氯 、 水 、 caesium carbonate 、 三乙胺 作用下， 以 四氢呋喃 、 甲苯 、 乙腈 为溶剂， 反应 78.0h， 生成 7-phenyl-1-[(4E)-5-phenylpent-4-enyl]bicyclo[3.1.1]heptan-6-one
  参考文献：
  名称：

  分子内烯酮-烯烃[2 + 2]环加成反应中烯烃之间的竞争：获胜需要什么？

  摘要：

  在开发一种在连续环加成步骤中使用烯酮的新合成方法的过程中，我们面临着一个竞争问题，即含有与多个反应伙伴相连的烯酮的分子。为了确定化学选择反应的电子和束缚要求，我们进行了一系列乙烯酮-烯烃[2 + 2]环加成竞争实验。这些实验是在含有两个具有不同束缚长度的相同烯烃或两个具有相同束缚长度但在电子上不同的烯烃的分子上进行的。我们证明了形成五元环的反应比六元环的反应快得多，并且计算出的分子内烯酮-烯烃[2 + 2]环加成物的哈米特常数ρ为-1.39。

  DOI：

  10.1021/jo0483466
• 作为产物：
  描述：

  (E)-5-phenylpent-4-en-1-yl 4-methylbenzenesulfonate 在 sodium iodide 作用下， 以 丙酮 为溶剂， 生成 (E)-(5-iodopent-1-enyl)benzene
  参考文献：
  名称：

  Regiochemical and stereochemical studies on halocyclization reactions of unsaturated sulfides

  摘要：

  The regiochemistry and stereochemistry for the halocyclization reactions of unsaturated benzyl sulfides have been examined as a function of tether length, type of unsaturation (carbon-carbon double bond versus carbon-carbon triple bond), substituents, and halogenating agent. Alkenyl sulfides were found to react with iodine or bromine at room temperature to give five-membered ring cycloadducts exclusively over those having four-membered rings, while for larger systems, six-membered ring products are formed preferentially over their five-membered ring isomers and exclusively over the seven-membered ring adducts. The endo- versus exo-regioselectivity of these alkenyl sulfide ring closures most likely reflects the difference in thermodynamic stabilities of the beta-halo sulfide cycloadducts, which are able to equilibrate via a common episulfonium intermediate. The efficiency of the cyclization process markedly drops off for these alkenyl sulfides as the tether length increases beyond four intervening carbon centers. Thus, while the halogenations of 3-butenyl sulfides and 4-pentenyl sulfides give high yields of cycloadducts, those of 5-hexenyl sulfides afford only small amounts of cyclized products and large quantities of acyclic dibromides. Conversely the reactions of acetylenic sulfides with iodine give uniformly high yields and regiochemical control regardless of the tether length. Thus, 3-butynyl and 4-pentynyl sulfides cyclize cleanly to the five-membered ring while 5-hexynyl sulfides give exclusively the six-membered ring, The products arising from these alkynyl sulfide ring closures are believed to be formed under kinetic control. The methodology has been applied to the synthesis of unusual bicyclic beta-lactams related to the penicillin family of antibiotics.

  DOI：

  10.1021/jo00125a038

文献信息

• SmI₂–H₂O-mediated 5-exo/6-exo lactone radical cyclisation cascades
  作者：Irem Yalavac、Sarah E. Lyons、Michael R. Webb、David J. Procter

  DOI：10.1039/c4cc05404k

  日期：——

  5-exo/6-exo lactone radical cyclisation cascades deliver carbo[5.4.0]bicycles in a diastereoselective, one-pot process using SmI₂ in the presence of H₂O.

  5-exo/6-exo内酯基自由基环化级联反应在一锅法中使用SmI₂和H₂O，选择性地合成carbo[5.4.0]双环化合物。
• Regioselective Epoxidations by Cytochrome P450 3A4 Using a Theobromine Chemical Auxiliary to Predictably Produce N-Protected β- or γ-Amino Epoxides
  作者：Vanja Polic、Kin Jack Cheong、Fabien Hammerer、Karine Auclair

  DOI：10.1002/adsc.201700637

  日期：2017.11.23

  N-Protected β- and γ-amino epoxides are useful chiral synthons. We report here that the enzyme cytochrome P450 3A4 can catalyze the formation of such compounds in a regio- and stereoselective manner, even in the presence of multiple double bonds or aromatic substituents. To this end, the theobromine chemical auxiliary is used not only to control the selectivity of the enzyme, but also as a masked amine

  N-保护的β-和γ-氨基环氧化物是有用的手性合成子。我们在此报告，即使存在多个双键或芳族取代基，细胞色素P450 3A4酶也可以区域和立体选择性方式催化此类化合物的形成。为此，可可碱化学助剂不仅用于控制酶的选择性，而且还用作掩蔽的胺，并促进产物的回收。可可碱可预测地将可可碱基团中第四个碳的双键定向环氧化。与大多数催化剂不同，选择性不取决于电子或空间因素，而是取决于烯烃相对于可可碱的位置。
• Effect of Double-Bond Substituents on the Rate of Cyclization of α-Carbomethoxyhex-5-enyl Radicals
  作者：Arthur Han、Tudor Spataru、John Hartung、Gang Li、Jack R. Norton

  DOI：10.1021/jo402499w

  日期：2014.3.7

  the corresponding acrylate esters 1 and the yields of cyclized products compared to the calculated rate constants. (The “cyclized products” include those from cyclohydrogenation, 4, and those from cycloisomerization, 9.) Two phenyl substituents on C6 (2i), or a phenyl and a methyl substituent (2g, 2h), increase the rate of cyclization, but a single phenyl substituent on C6 produces a greater increase

  已经计算出速率常数，并将其与实验结果进行比较，以对在C6上具有各种取代基的1-甲氧基-1-甲基-5-己烯基自由基（2）进行环化。通过DFT在B3LYP / 6-311 ++ G **的理论水平上进行了计算。它们显示了C5和自由基中心之间的相当大的相互作用，即使在所有自由基2的基态下也是如此。在实验上，自由基是通过H •转移至相应的丙烯酸酯1生成的，并将环化产物的产率与计算出的速率常数进行比较。（“环化产物”包括来自环氢化的产物4和来自环异构化的产物9。）C6（2i）上的两个苯基取代基，或苯基和甲基取代基（2g，2h）提高环化率，但C6上的单个苯基取代基产生更大的环化。计算表明，两个苯基取代基在过渡态中被扭曲以进行环化，而单个苯基取代基在该过渡态中保持平坦。C6上的甲基取代基与单个苯基一起导致苯基在过渡态发生扭曲，并使环化的速率常数降低到H / Ph-取代的2e，2f之下。
• Lewis acid promoted intramolecular (3 + 2) ‘cycloadditions’ of methyleneaziridines with alkene and alkyne acceptors
  作者：Karen Griffin、Cyril Montagne、Cam Thuy Hoang、Guy J. Clarkson、Michael Shipman

  DOI：10.1039/c1ob06578e

  日期：——

  2-Methyleneaziridines can be tethered to a variety of alkene or alkyne acceptors through the saturated carbon of the heterocyclic ring by application of a simple lithiation/alkylation sequence (8 examples, 31–59%). Treatment of the resultant alkene bearing substrates with BF3·OEt2 leads to cis-octahydrocyclopenta[c]pyrroles in which up to four contiguous stereocentres are created in a diastereocontrolled

  可以通过应用简单的锂化/烷基化顺序（8个实例，31-59％），通过杂环的饱和碳将2-亚甲基氮丙啶束缚到各种烯烃或炔烃受体上。用BF 3 ·OEt 2处理所得的带有烯烃的底物导致顺式-八氢环戊基[c]吡咯，其中在还原后，以非对映控制的方式产生多达四个连续的立体中心。使用基于炔的底物，通过最初形成的双烯胺的快速互变异构化来制备2,4,5,6-四氢环戊[c]吡咯。这些（3 + 2）'环加成'逐步通过2-氨基烯丙基阳离子进行的证据。
• Thornton, Aaron R.; Martin, Veronique I.; Blakey, Simon B., Journal of the American Chemical Society, 2009, vol. 131, p. 2434 - 2435
  作者：Thornton, Aaron R.、Martin, Veronique I.、Blakey, Simon B.

  DOI：——

  日期：——