2-(bromomethyl)-1,5-hexadiene | 152705-72-1

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机溴化物
• 英文名称: 2-(bromomethyl)-1,5-hexadiene
• 英文别名: 2-(Bromomethyl)hexa-1,5-diene
• CAS: 152705-72-1
• 化学式: C₇H₁₁Br
• 分子量: 175.068
• InChiKey: VZAXJVWEBKIVHH-UHFFFAOYSA-N

物化性质

• 沸点：
  179.2±19.0 °C(Predicted)
• 密度：
  1.188±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  8
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  2-(bromomethyl)-1,5-hexadiene 在 四氯化碳 、 正丁基锂 、 四甲基乙二胺 、 三苯基膦 作用下， 反应 11.5h， 生成 2,5,8,11,14-pentamethylideneoctadec-17-en-1-ol
  参考文献：
  名称：

  Palladium-catalyzed cyclizations of polyenynes. A palladium zipper

  摘要：

  The cycloisomerization of polyenynes with a catalyst derived from Pd(0), acetic acid, and a ligand to polycycles depends upon the juxtaposition of unsaturation. The process involves the stages of initiation (by addition of Pd-H to an acetylene), propagation (by intramolecular carbopalladation), and termination (by beta-hydrogen elimination). With 2-homopropargylated 1,5- and 1,6-dienes, monocyclizations via 5-exo and 6-endo modes dominate with the ratio dependent upon ligand. The 5-exo mode is favored by tri-o-tolylphosphine, whereas triphenylstibine favors the 6-endo mode. On the other hand, a 3-homoallyl-3-homopropargylcyclopentene undergoes smooth bicyclization even when triphenylphosphine is used as ligand. Combining Pd(0)-catalyzed allylic alkylation to make the substrates with Pd(0)-catalyzed cycloisomerization simplifies triquinane and azatriquinane synthesis. A2-allyl-2-homopropargyl-1-methylenecycloalkane array cycloisomerizes to [4.3.3]propellanes and [3.3.3]propellanes. Methallyl alcohol serves as a basic building block to construct acyclic substrates for construction of spirocycles. Both terminal and internal acetylenes serve as suitable initiators provided the proper ligand is employed. With a terminal acetylene as initiator, triphenylphosphine proves satisfactory, but an internal acetylene requires triphenylstibine. High diastereoselectivity may accompany formation of the spirocycle. Increasing the number of double bonds increases the number of rings formed. Substrates bearing 3, 4, 5, 6, and 7 double bonds generate polyspiranes consisting of 3, 4, 5, 6, and 7 rings. The regio- and diastereoselectivity may be understood on the basis of a conformational analysis of the reactive intermediate. This atom economical approach for construction of polycycles can be considered as the equivalent of a palladium zipper in which the pi orbitals are the teeth and the palladium complex is the tab. Closing the zipper stitches the pi bonds into sigma bonds with creation of the polycycles.

  DOI：

  10.1021/ja00074a008
• 作为产物：
  描述：

  2-methylene-5-hexen-1-ol 在 三溴化磷 作用下， 以 乙醚 为溶剂， 反应 10.0h， 以39%的产率得到2-(bromomethyl)-1,5-hexadiene
  参考文献：
  名称：

  Ligand‐Controlled Palladium‐Catalyzed Regiodivergent Defluorinative Allylation of gem ‐Difluorocyclopropanes via σ‐Bond Activation

  摘要：

  Comprehensive SummaryMonofluoroalkenes are important and versatile privileged components in pharmacologically relevant molecules. Here, we report a method for the selective construction of these compounds in a diversity‐oriented fashion through regiodivergent cross‐coupling of gem‐difluorocyclopropanes with allylboronates by employing a palladium catalyst with two different ligands, in which gem‐difluorocyclopropanes were used as allyl electrophiles by C—C and C—F bond activation. In the presence of 2‐biphenylyl(diphenyl)phosphine as ligand, the linear‐selective allyl–allyl bond formation is highly obtained, while utilizing the sterically hindered BrettPhos (dicyclohexyl[3,6‐dimethoxy‐2',4',6'‐tris(1‐methylethyl)[1,1'‐biphenyl]‐2‐yl]phosphine) as the ligand favors the generation of the branched‐selective product. Experimental and computational studies investigated the key steps of the cross‐coupling reactions, revealing the origin of the ligand‐controlled regiodivergence.

  DOI：

  10.1002/cjoc.202200307

文献信息

• Synthesis of Polycyclic Imines by Palladium-Catalyzed Domino Cyclization of Di- and Trienyl Ketone<i>O</i>-Pentafluorobenzoyloximes
  作者：Shazia Zaman、Mitsuru Kitamura、Koichi Narasaka

  DOI：10.1246/bcsj.76.1055

  日期：2003.5

  Various cyclic imines, such as spiro imines and a fused bicyclic imine, are synthesized from dienyl and trienyl ketone O-pentafluorobenzoyloximes by the domino amino-Heck reaction. Treatment of the oximes with a catalytic amount of Pd(PPh3)4 and triethylamine gives polycyclic imines in high yields via alkylideneaminopalladium(II) intermediates generated in situ by the oxidative addition of the oximes

  各种环状亚胺，例如螺亚胺和稠合双环亚胺，是由二烯基和三烯基酮 O-五氟苯甲酰肟通过多米诺氨基-Heck 反应合成的。用催化量的 Pd(PPh3)4 和三乙胺处理肟，通过将肟氧化加成到 Pd(0) 络合物中原位生成的亚烷基氨基钯 (II) 中间体，以高产率得到多环亚胺。
• Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization–Carbonylation–Alkynylation
  作者：Youai Qiu、Bin Yang、Can Zhu、Jan-E. Bäckvall

  DOI：10.1021/jacs.6b09240

  日期：2016.10.26

  A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C–C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an

  已经开发了一种高选择性级联反应，允许二烯二烯直接转化为作为单一非对映异构体的螺环丁烯（螺 [3.4] 辛烯）。该反应涉及形成总共四个 C-C 键，并通过钯催化的氧化转化进行，并插入烯烃、烯烃和一氧化碳。在略有不同的反应条件下，发生额外的 CO 插入以产生螺 [4.4] 壬烯，并形成总共五个 C-C 键。
• Palladium(II)-Catalyzed Oxidative Cascade Cyclization Reactions of Anilides and Anilines: Scope and Mechanistic Investigations
  作者：Kai-Tai Yip、Dan Yang

  DOI：10.1002/asia.201100242

  日期：2011.8.1

  catalyst system and molecular oxygen as a green oxidant, acrylanilides and N‐allylanilines undergo oxidative cascade cyclization to form heterocyclic rings in high yields. This methodology is applicable to acrylanilides of different substitution patterns on olefinic units. Mechanistic studies revealed that cyclization of acrylanilides proceeded through an intramolecular syn‐amidopalladation pathway. The

  以Pd（OAc）2 /吡啶为催化剂体系，以分子氧为绿色氧化剂，丙烯酰苯胺和N-烯丙基苯胺经过氧化级联环化反应以高产率形成杂环。该方法学适用于烯烃单元上不同取代方式的丙烯酰苯胺。机理研究表明，丙烯酰胺的环化过程是通过分子内合成来进行的。-泛乳化途径。酰胺基palladation的可逆性质是一个“清除过程”，以防止在催化循环中途发生β-氢化物消除，从而有利于级联环化产物的形成。另外，σ-烷基钯物质与链状烯烃CC双键之间的内部配位似乎也不利于β-氢化物的消除。
• Copper-Mediated Trifluoromethylation–Allylation of Arynes
  作者：Xinkan Yang、Gavin Chit Tsui

  DOI：10.1021/acs.orglett.8b00101

  日期：2018.2.16

  An unprecedented three-component copper-mediated vicinal trifluoromethylation–allylation of arynes is described. A wide range of structurally diverse trifluoromethylated allylarenes can be quickly assembled in one step. The application of the method has been demonstrated in the expedient synthesis of the CF3-containing analogue of the antispasmodic drug papaverine. The new reactivity of the [CuCF3]

  描述了史无前例的三组分铜介导的邻位三氟甲基化-芳烃的烯丙基化。一步就可以快速组装多种结构多样的三氟甲基化烯丙基芳烃。该方法的应用已在合成抗痉挛药物罂粟碱的含CF 3的类似物中得到证明。由廉价的工业副产物氟仿生成的[CuCF 3 ]试剂具有新的优势，具有独特的优势。
• Catalyst and pressure dependent reductive cyclizations for the diastereo-selective synthesis of hexahydropyrrolo[1,2-<i>a</i>]quinoline-5-carboxylic esters
  作者：Richard A. Bunce、James E. Schammerhorn、Legrande M. Slaughter

  DOI：10.1002/jhet.5570430613

  日期：2006.11

  A diastereoselective synthesis of 1,2,3,3a,4,5-hexahydropyrrolo[1,2-a]quinoline-5-carboxylic esters has been developed using a tandem reduction-double reductive amination reaction. The nitro dicarbonyl cyclization substrates were synthesized by alkylation of methyl (2-nitrophenyl)acetate with 2-bromomethyl-1,5-hexadiene derivatives, followed by ozonolysis. Catalytic hydrogenation of each substrate

  利用串联还原-双还原胺化反应，开发了一种非对映选择性的1,2,3,3a，4,5-六氢吡咯并[1,2- a ]喹啉-5-羧酸酯。硝基二羰基环化底物的合成方法是，将（2-硝基苯基）乙酸甲酯与2-溴甲基-1,5-己二烯衍生物进行烷基化，然后进行臭氧分解。每种底物的催化加氢给出了目标杂环，以及脱酰基产物和由侧链羰基捕获中间羟胺所产生的加合物。产物比率随催化剂和氢气压力而显着变化。标题化合物的环化反应具有很高的非对映选择性，产生每种六氢吡咯并[1,2- a] -喹啉如与清一色单一立体异构体顺式几何形状。在先前的杂环研究中未观察到竞争过程，但可归因于系统中更大的应变，这减慢了最终的环闭合。