3-[(4SR,5SR)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-ene-4-yl]prop-2-yn-1-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-[(4SR,5SR)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-ene-4-yl]prop-2-yn-1-ol
• 英文别名: 3-[(4SR,5SR)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-en-4-yl]prop-2-yn-1-ol；3-[(4S,5S)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-en-4-yl]prop-2-yn-1-ol
• 化学式: C₁₃H₁₇BrO₃
• 分子量: 301.18
• InChiKey: CDCXQDCJQXJXPR-WCQYABFASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  17
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-[(4SR,5SR)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-ene-4-yl]prop-2-yn-1-ol 在 manganese(IV) oxide 、 sodium tetrahydroborate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 0.25h， 生成 N-[3-[(4S,5S)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-en-4-yl]prop-2-ynyl]aniline
  参考文献：
  名称：

  新型钯催化的级联反应：4- exo- dig环碳烷基缩合反应，随后是铃木–宫浦或Sonogashira交叉偶联

  摘要：

  在本文中，我们描述了使用新的级联反应获得二烯和三苯炔的新途径：4- exo- dig环碳杂钯化，然后是Suzuki-Miyaura或Sonogashira交叉偶联。

  DOI：

  10.1002/adsc.201100465
• 作为产物：
  描述：

  聚合甲醛 、 (4SR,5SR)-6-bromo-4-ethynyl-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-ene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.5h， 以87%的产率得到3-[(4SR,5SR)-6-bromo-2,2-dimethyl-1,3-dioxaspiro[4.5]dec-6-ene-4-yl]prop-2-yn-1-ol
  参考文献：
  名称：

  一种新的钯催化级联反应，用于合成应变芳族多环。

  摘要：

  描述了两个新的钯催化的级联反应，涉及4-exo-dig环碳钯反应。已显示这些过程可在一个步骤中将溴代二炔和溴代二炔转化为应变的芳族化合物。

  DOI：

  10.1021/ol702855h

文献信息

• An Expeditious and Atom-Economical Synthesis of a New Generation of Substituted [4.6.4.6]Fenestradienes
  作者：Mélanie Charpenay、Aïcha Boudhar、Gaëlle Blond、Jean Suffert

  DOI：10.1002/anie.201107934

  日期：2012.4.27

  With finesse and strain: Highly strained derivatives of fenestranes, [4.6.4.6]fenestradienes, have been prepared using a remarkable reaction cascade featuring a 4‐exo‐dig cyclocarbopalladation, a Sonogashira‐type coupling, a regioselective alkynylation, and an 8π/6π electrocyclization sequence.

  具有精细和应变性：芬内酯的高应变衍生物，[4.6.4.6]苯丙二烯，是使用非凡的反应级联反应制备的，该反应级联反应具有4- exo- dig环碳杂钯，Sonogashira型偶联，区域选择性炔基化和8π/6π电环化序列。
• Expeditious cascade reactions: controlled syntheses of fenestradienes and cyclooctatrienes under palladium catalysis
  作者：Mélanie Charpenay、Aicha Boudhar、Catherine Hulot、Gaëlle Blond、Jean Suffert

  DOI：10.1016/j.tet.2013.05.089

  日期：2013.9

  carbopalladation/Sonogashira coupling tandem reaction, and a subsequent P-2 Ni induced semi-hydrogenation. This leads to a first generation of cyclooctatrienes and [4.6.4.6]fenestradienes. Next, the second approach will be presented, in which the second generation of these compounds is accessed in a one-pot reaction including five steps, starting from the same alkenyl bromide compounds. These methods

  钯环化级联代表了一种精巧的方法，可以以最少的步骤访问复杂的多环支架。在此，我们提供了两种新方法的完整说明，其中包括这类级联反应，每种方法都会产生两种有吸引力的化合物，即环辛烯和[4.6.4.6]苯并菲。读者将首先发现一种策略，该方法需要从烯基溴开始的三个步骤，这是基于第一个4- exo-挖掘碳巴巴定/ Sonogashira偶联串联反应，然后进行P-2 Ni诱导的半氢化反应。这导致了第一代环辛烯和[4.6.4.6]苯雌二醇。接下来，将介绍第二种方法，其中从同一个链烯基溴化物化合物开始，通过一站式反应（包括五个步骤）访问这些化合物的第二代。这些方法在原子经济，易于使用的条件及其范围可变性方面具有吸引力。
• Hopping of Palladium: Access to Original Polycyclic Structures Containing Three-, Four-, Five- and Six-Membered Rings
  作者：Jean Suffert、Gaëlle Blond、Nayan Ghosh、Carmen Maiereanu

  DOI：10.1055/s-0036-1588658

  日期：——

  The syntheses of new scaffolds containing small strained rings are described via an original domino reaction. The process works efficiently and selectively via 4-exo-dig/5- or 6-exo-trig/3-exo-trig cyclocarbopalladations followed by a β-hydride elimination. During this cascade, the palladium moves several times along the carbon structure for the creation of three new C–C bonds and three new rings.

  包含小应变环的新支架的合成是通过原始多米诺骨牌反应描述的。该过程通过 4-exo-dig/5- 或 6-exo-trig/3-exo-trig 环碳钯化和 β-氢化物消除有效且有选择性地工作。在这个级联过程中，钯沿着碳结构移动数次，以产生三个新的 C-C 键和三个新环。
• Synthesis of [4.6.4.6]Fenestradienes and [4.6.4.6]Fenestrenes Based on an 8π−6π-Cyclization-Oxidation Cascade
  作者：Catherine Hulot、Gaëlle Blond、Jean Suffert

  DOI：10.1021/ja800691c

  日期：2008.4.1

  compounds of synthetic and theoretical interest are a class of tetracyclic skeletons, defined as doubly a,a'-bridged spiroalkanes. The reported results are focused on the synthesis of new and original [4.6.4.6]fenestradienes 3a-f and [4.6.4.6]fenestrenes 4a-e. Our approach implies the formation of this tetracyclic structure by a reaction cascade, based on consecutive transformations starting from the trienyne

  Fenestrane 被认为是一个特别具有挑战性的合成目标，最近只有少数合成报道。这些具有合成和理论意义的稀有化合物是一类四环骨架，定义为双 a,a'-桥连螺烷烃。报告的结果集中在新的和原始的 [4.6.4.6] fenestradienes 3a-f 和 [4.6.4.6]fenestrenes 4a-e 的合成上。我们的方法意味着通过反应级联形成这种四环结构，基于从三烯炔 1a-f 开始的连续转化：在室温下使用 P-2 镍催化剂进行初始软氢化，然后是旋转 8p 电环化和旋转6p 电环化和最终氧化。本通讯中描述了此类新化合物的几个例子。
• Understanding the Torquoselectivity in 8π-Electrocyclic Cascade Reactions: Synthesis of Fenestradienes versus Cyclooctatrienes
  作者：Catherine Hulot、Shadi Amiri、Gaëlle Blond、Peter R. Schreiner、Jean Suffert

  DOI：10.1021/ja903914r

  日期：2009.9.23

  Unusual and novel polycyclic cyclooctatrienes, fenestradienes, and fenestrenes form readily from trienynes depending on the structure of the starting trienynes and the reaction conditions. The experimentally observed high torquoselectivities and complete diastereoselectivities of the 8 pi-electrocyclization products have been thoroughly studied using density functional computations at B3PW91/6-31G(d,p). The different P- and M-helical topologies for the Mobius aromatic transition structures are the origin of the observed torquoselectivities in the cyclooctatrienes. The P-helical topologies direct the newly formed single bonds into a favorable equatorial position of the neighboring cycloalkane moieties (X = ring size) that retain their most stable conformation. The M-helical transition structures lead to an axial connection for the smaller rings (X = 4-6) and an equatorial connection for the seven- and eight-membered cycloalkanes. This leads to unfavorable conformations for the larger cycloalkane moieties. Experiments and computations show that for trienynes involving small neighboring cycloalkane groups (X = 4-6) M-helical topology is preferred toward cyclooctatrienes and in the following the corresponding fenestradienes can be formed as kinetic or even thermodynamic products; they convert to their more stable cyclooctatriene valence isomers derived from P-helical transition structures at higher temperatures. For larger cycloalkane moieties with more conformational flexibility only cyclooctatrienes with torquoselectivities derived from P-helical transition structures form.