4,4-bis(methoxymethyl)hepta-1,6-diene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4,4-bis(methoxymethyl)hepta-1,6-diene
• 英文别名: 4,4-di(methoxymethyl)-1,6-heptadiene；(MeOCH2)2C(CH2CH=CH2)2；4,4-Bis(methoxymethyl)-1,6-heptadiene
• 化学式: C₁₁H₂₀O₂
• 分子量: 184.279
• InChiKey: UQXVOOKVENLTCN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4,4-bis(methoxymethyl)hepta-1,6-diene 在 正丁基锂 、 二氯二茂锆 、 氯碘甲烷 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.5h， 以77%的产率得到(+/-)-(3R,4R)-3-(iodomethyl)-1,1-bis(methoxymethyl)-4-methylcyclopentane
  参考文献：
  名称：

  Ring expansion of 5- to 6-member zirconacycles by carbenoid insertion

  摘要：

  A wide range of carbenoids (1-lithio-1-halo species), including those with alpha-SiR3, OEt, SPh, SO2Ph, P(O)(OEt)(2), and CN substituents, insert into 5-member zirconacycles (saturated and unsaturated, mono- and bi-cyclic) to afford functionalized 6-member zirconacycles. 1-Lithio-1-haloalkenes insert to afford 6-member zirconacycles with an alkylidene substituent next to the metal. Unexpected double insertion of some carbenoids, and evidence for endocylic beta-hydride transfer processes provide additional mechanistic interest. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2003.09.056

文献信息

• CATALYST FOR OLEFIN POLYMERIZATION AND METHOD OF PREPARATION THEREOF
  申请人：Wang Licai

  公开号：US20110301385A1

  公开（公告）日：2011-12-08

  A catalyst for olefin polymerization and method of preparing the same are disclosed.

  揭示了一种烯烃聚合的催化剂及其制备方法。
• Tandem Insertion of Halocarbenoids and Lithium Acetylides into Zirconacycles: A Novel Rearrangement to Zirconium Alkenylidenates by β-Addition to an Alkynyl Zirconocene
  作者：Jozef Stec、Emma Thomas、Sally Dixon、Richard J. Whitby

  DOI：10.1002/chem.201002962

  日期：2011.4.18

  Tandem insertion of 1,1‐dihalo‐1‐lithio species (halocarbenoids) and lithium alkynides into zirconacyclopentenes and zirconcyclopentanes affords carbocyclic products in high yields via an unusual rearrangement that probably involves addition of an organolithium species to the β‐position of a zirconium–alkyne complex to give an alkenylidene–zirconate species. A wide variety of cyclopentanoid organic

  将1,1–二卤代1–硫代化合物（卤代类固醇）和炔属锂串联插入到氧化锆环戊烯和锆环戊烷中可以通过不寻常的重排提供高收率的碳环产物，该重排可能涉及将有机锂物种添加到锆的β位上。炔烃复合物，可得到烯基-锆酸酯。使用这种多组分偶联剂，可以高产率快速组装各种各样的环戊烷类有机结构。在某些情况下，主要的副反应是β-氢化物消除中间的环戊基或环戊烯基锆茂。
• Ruthenium(ii)-catalysed cycloisomerisation of 1,6-dienes by focused microwave dielectric heating: improved rates and selectivities leading to exo-methylenecyclopentanes
  作者：Ian J. S. Fairlamb、Gerard P. McGlacken、Felix Weissberger

  DOI：10.1039/b513798e

  日期：——

  We herein report the effect of microwave dielectric heating in the Ru-catalysed cycloisomerisation of 1,6-dienes. Substantially improved reaction rates are attained for a series of 1,6-diene substrates, with equivalent or higher isomeric purity than conventional thermal heating.

  我们在此报告了微波介电加热在钌催化的1,6-二烯环异构化中的影响。对于一系列1,6-二烯底物，反应速度显著提高，并且异构体纯度与传统热加热相当或更高。
• A thiyl radical mediated cascade sequence for the co-cyclisation of 1,6-hexadienes with sulfur atom transfer
  作者：David C Harrowven、Joanne C Hannam、Matthew C Lucas、Nicola A Newman、Peter D Howes

  DOI：10.1016/s0040-4039(00)01701-9

  日期：2000.11

  The paper describes a method for effecting the co-cyclisation of 1,6-dienes with concomitant sulfur atom transfer. The key step is a cascade reaction involving the addition of a thiyl radical to an alkene, cyclisation through a chair-like transition state and termination by homolytic substitution at sulfur. It has been used to synthesise a broad range of fused thiabicyclo[3.3.0]octanes.

  该论文描述了一种伴随硫原子转移而实现1，6-二烯共环化的方法。关键步骤是级联反应，涉及将硫烷基自由基加到烯烃上，通过椅状过渡态进行环化，并通过在硫上的均质取代而终止。它已被用来合成各种稠合的硫代双环[3.3.0]辛烷。
• Palladium-Catalyzed Asymmetric Diene Cyclization/Hydrosilylation Employing Functionalized Silanes and Disiloxanes
  作者：Tao Pei、Ross A. Widenhoefer

  DOI：10.1021/jo015724n

  日期：2001.11.1

  diallylmalonate (1) and other functionalized 1,6-dienes in the presence of a catalytic 1:1 mixture of (N-N)Pd(Me)Cl [N-N = (R)-(+)-4-isopropyl-2-(2-pyridinyl)-2-oxazoline] [(R)-2] and NaBAr(4) [Ar = 3,5-C(6)H(3)(CF(3))(2)] to form the corresponding silylated cyclopentanes in good yield with high diastereoselectivity. The enantioselectivity of cyclization/hydrosilylation of 1 with disiloxanes and functionalized

  HSiMe（2）CH（x）Ph（3-x）（x = 1或2）形式的五取代二硅氧烷和硅烷与二烯丙二酸二甲酯（1）和其他功能化的1,6-二烯在催化1存在下反应：1（NN）Pd（Me）Cl [NN =（R）-（+）-4-异丙基-2-（2-吡啶基）-2-恶唑啉] [（R）-2]和NaBAr（4 ）[Ar = 3,5-C（6）H（3）（CF（3））（2）]以高收率和高非对映选择性形成相应的甲硅烷基化环戊烷。1在20摄氏度下与二硅氧烷和官能化硅烷的1的环化/氢化硅烷化的对映选择性按以下顺序增加：HSiMe（2）OSiMe（3）（75％ee）