7-bromohepta-1,3-diene | 103131-23-3

• 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: 7-bromohepta-1,3-diene
• CAS: 103131-23-3
• 化学式: C₇H₁₁Br
• 分子量: 175.068
• InChiKey: CLYXFXGAMNZAOQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 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：

  7-bromohepta-1,3-diene 在 sodium periodate 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醇 、 苯 为溶剂， 反应 49.0h， 生成 cis-2-allyltetrahydrothiophene 1-oxide
  参考文献：
  名称：

  Altering the Stereochemistry of Allylation Reactions of Cyclic .alpha.-Sulfinyl Radicals: Effects of Solvents and Lewis Acids

  摘要：

  Full details of the stereochemical outcome of the allylation of the tetrahydrothiophene-2-yl 1-oxide radical in different solvents and in the presence of Lewis acids are reported. Corrections of the cis/trans ratios initially reported in the original communication are presented and the origin for the systematic overestimation of the ratio was found to be the decomposition of the minor cis diastereoisomer during the GC analysis. However, the originally reported stereoselectivity enhancements in the presence of Lewis acids are still valid, although the effects are of smaller amplitudes. The conclusions about an intermediate oxygen-complexed a-sulfinyl radical stand. We report that the very bulky and oxygenophilic methylaluminum diphenoxides (MAD and MABR), recently intoduced by Yamamoto, are perfectly compatible with radical reactions and provide exceptional levels of stereocontrol (up to 98:2) when used stoichiometrically. A good level of stereoselectivity (90:10) was reached by using a catalytic amount of MABR (10%). The yields and the stereoselectivities of the radical allylations compare favorably with the nucleophilic allylation af the deprotonated tetrahydrothiophene 1-oxide.

  DOI：

  10.1021/jo00092a010
• 作为产物：
  描述：

  7-<(tert-butyldimethylsilyl)oxy>-1,3-heptadiene 在 triphenylphosphine dibromide 1:1 addition complex 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 以69%的产率得到7-bromohepta-1,3-diene
  参考文献：
  名称：

  Altering the Stereochemistry of Allylation Reactions of Cyclic .alpha.-Sulfinyl Radicals: Effects of Solvents and Lewis Acids

  摘要：

  Full details of the stereochemical outcome of the allylation of the tetrahydrothiophene-2-yl 1-oxide radical in different solvents and in the presence of Lewis acids are reported. Corrections of the cis/trans ratios initially reported in the original communication are presented and the origin for the systematic overestimation of the ratio was found to be the decomposition of the minor cis diastereoisomer during the GC analysis. However, the originally reported stereoselectivity enhancements in the presence of Lewis acids are still valid, although the effects are of smaller amplitudes. The conclusions about an intermediate oxygen-complexed a-sulfinyl radical stand. We report that the very bulky and oxygenophilic methylaluminum diphenoxides (MAD and MABR), recently intoduced by Yamamoto, are perfectly compatible with radical reactions and provide exceptional levels of stereocontrol (up to 98:2) when used stoichiometrically. A good level of stereoselectivity (90:10) was reached by using a catalytic amount of MABR (10%). The yields and the stereoselectivities of the radical allylations compare favorably with the nucleophilic allylation af the deprotonated tetrahydrothiophene 1-oxide.

  DOI：

  10.1021/jo00092a010

文献信息

• Palladium(II) Catalyzed C–H Functionalization Cascades for the Diastereoselective Synthesis of Polyheterocycles
  作者：Michael S. Watt、Kevin I. Booker-Milburn

  DOI：10.1021/acs.orglett.6b02947

  日期：2016.11.4

  C–H activation offers huge potential in the generation of complex structures from simple starting materials. Herein we report the development of a highly diastereoselective palladium(II) catalyzed C–H functionalization cascade to produce novel, unsaturated polyheterocycles from simple diene-tethered heterocyclic starting materials. The reaction is applicable to both indole and pyrrole based substrates

  C–H活化在从简单的起始原料生成复杂结构方面提供了巨大的潜力。在本文中，我们报道了由非对映选择性的钯（II）催化的C–H官能化级联反应的发展，该反应由简单的由二烯系链的杂环原料生产出新颖的，不饱和的多杂环。该反应适用于基于吲哚和吡咯的底物，并能耐受杂芳族核周围的各种官能团取代。多杂环产物形成为单一的非对映异构体，并且在一个步骤中形成了两个新的立体中心。
• Rh(III)-Catalyzed Intra- and Intermolecular 3,4-Difunctionalization of 1,3-Dienes via Rh(III)-π-Allyl Amidation with 1,4,2-Dioxazolones
  作者：Finn Burg、Tomislav Rovis

  DOI：10.1021/acscatal.2c02537

  日期：2022.8.5

  We herein report a modular strategy, which enables Rh(III)-catalyzed diastereoselective 3,4-amino oxygenation and diamination of 1,3-dienes using different O- and N-nucleophiles in combination with readily available 3-substituted 1,4,2-dioxazolones (78 examples, 37–91% yield). Previous attempts to functionalize the internal double bond rested on the use of plain alcoholic solvents as nucleophilic coupling

  我们在此报告了一种模块化策略，该策略能够使用不同的O-和N-亲核试剂与容易获得的 3-取代 1,4 相结合，实现 Rh(III) 催化的非对映选择性 3,4-氨基氧化和 1,3-二烯的二胺化。 2-二恶唑酮（78 个实例，产率 37-91%）。以前对内部双键进行官能化的尝试依赖于使用普通醇溶剂作为亲核偶联伙伴，从而极大地限制了这种转化的范围。我们现在已经确定六氟异丙醇是一种非亲核溶剂，允许使用多种亲核试剂并大大扩展了范围，包括前所未有的氨基羟基化，以在 1,3-二烯上选择性地安装有价值的、未受保护的 β-氨基醇。此外，各种精制醇被证明是相容的，提供了获取复杂有机分子的独特途径。最后，该方法用于一系列分子内反应，以提供有价值的氮杂环以及γ-和δ-内酯。
• Intramolecular Carboamination of Aminodienes to <i>N</i>‐Heterocycles via C−N Bond Activation
  作者：Xuyang Yan、Bangkui Yu、Hongchi Liu、Hanmin Huang

  DOI：10.1002/anie.202316563

  日期：2024.2.19

  An expedient annulative carboamination of aminodienes via C−N bond activation enabled by a unique I2/Ni or benzyl halide/Ni-catalytic system is described. This reaction features high atom-economy and provides rapid access to a range of pyrrolidines, piperidines, and tetrahydroisoquinoline derivatives.

  描述了一种通过独特的 I 2 /Ni 或苄基卤/Ni 催化系统实现的 CN 键活化对氨基二烯进行便利的环碳胺化。该反应具有高原子经济性，可以快速获得一系列吡咯烷、哌啶和四氢异喹啉衍生物。
• Altering the Stereochemistry of Allylation Reactions of Cyclic .alpha.-Sulfinyl Radicals: Effects of Solvents and Lewis Acids
  作者：Philippe Renaud、Nadira Moufid、Lung Huang Kuo、Dennis P. Curran

  DOI：10.1021/jo00092a010

  日期：1994.7

  Full details of the stereochemical outcome of the allylation of the tetrahydrothiophene-2-yl 1-oxide radical in different solvents and in the presence of Lewis acids are reported. Corrections of the cis/trans ratios initially reported in the original communication are presented and the origin for the systematic overestimation of the ratio was found to be the decomposition of the minor cis diastereoisomer during the GC analysis. However, the originally reported stereoselectivity enhancements in the presence of Lewis acids are still valid, although the effects are of smaller amplitudes. The conclusions about an intermediate oxygen-complexed a-sulfinyl radical stand. We report that the very bulky and oxygenophilic methylaluminum diphenoxides (MAD and MABR), recently intoduced by Yamamoto, are perfectly compatible with radical reactions and provide exceptional levels of stereocontrol (up to 98:2) when used stoichiometrically. A good level of stereoselectivity (90:10) was reached by using a catalytic amount of MABR (10%). The yields and the stereoselectivities of the radical allylations compare favorably with the nucleophilic allylation af the deprotonated tetrahydrothiophene 1-oxide.