isopropyltriphenylphosphonium bromide

• 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: isopropyltriphenylphosphonium bromide
• 英文别名: Bromo-triphenyl-propan-2-yl-lambda5-phosphane；bromo-triphenyl-propan-2-yl-λ5-phosphane
• 化学式: C₂₁H₂₂BrP
• 分子量: 385.283
• InChiKey: QSMXKYMUPWTVCV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 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：

  isopropyltriphenylphosphonium bromide 生成 triphenylphosphonio-1-methylethanide
  参考文献：
  名称：

  GOERING, H. L.;KANTNER, S. S.;TSENG, CHUNG, CHYI, J. ORG. CHEM., 1983, 48, N 5, 715-721

  摘要：

  DOI：
• 作为产物：
  描述：

  Methyl 2-[bromo(triphenyl)-lambda5-phosphanyl]propanoate 以89%的产率得到
  参考文献：
  名称：

  DING, WEI-YU;CAI, WEN;PU, JIA-QI;SHEN, WEI-PING;DAI, JIN-SHAN, ACTA CHIM. SIN., 1985, 43, N 1, 53-56

  摘要：

  DOI：

文献信息

• Oxidative Cleavage of Alkenes by O₂ with a Non-Heme Manganese Catalyst
  作者：Zhiliang Huang、Renpeng Guan、Muralidharan Shanmugam、Elliot L. Bennett、Craig M. Robertson、Adam Brookfield、Eric J. L. McInnes、Jianliang Xiao

  DOI：10.1021/jacs.1c05757

  日期：2021.7.7

  however. There are only a small number of known synthetic metal catalysts that allow for the oxidative cleavage of alkenes at an atmospheric pressure of O2, with very few known to catalyze the cleavage of nonactivated alkenes. In this work, we describe a light-driven, Mn-catalyzed protocol for the selective oxidation of alkenes to carbonyls under 1 atm of O2. For the first time, aromatic as well as various

  C=C双键与分子氧的氧化裂解产生羰基化合物是化学和药物合成中的一个重要转化。在自然界中，含有第一排过渡金属的酶，特别是血红素和非血红素铁依赖性酶，在环境条件下很容易激活 O 2并以极其精确的方式氧化裂解 C=C 键。然而，该反应对合成化学家来说仍然具有挑战性。只有少数已知的合成金属催化剂允许在 O 2大气压下氧化裂解烯烃，很少有人知道催化未活化烯烃的裂解。在这项工作中，我们描述了一种光驱动、Mn 催化的协议，用于在 1 个大气压的 O 2下将烯烃选择性氧化为羰基化合物。首次使用第一排生物相关金属催化剂，在清洁、温和的条件下，可以将芳香族和各种未活化的脂肪族烯烃氧化成酮和醛。此外，该协议显示出非常好的功能组耐受性。机理研究表明，Mn-oxo 物种，包括不对称的混合价双 (μ-oxo)-Mn(III,IV) 络合物，参与氧化，溶剂甲醇参与 O 2活化，导致oxo 物种的形成。
• [3,3]Sigmatropic ring expansion of cyclic thionocarbonates. 9. total synthesis of (±)-yellow scale pheromone via 10-membered thiolcarbonate
  作者：Shinya Harusawa、Shigetaka Takemura、Hirotaka Osaki、Ryuji Yoneda、Takushi Kurihara

  DOI：10.1016/s0040-4020(01)87241-0

  日期：1993.8

  (±)-Yellow scale pheromone 1 has been synthesized via the route illustrated in Scheme 1. The [3,3]sigmatropic ring expansion of 8-membered thionocarbonate 4 exclusively produced the (Z)-10-membered thiolcarbonate 3, which was transformed via three steps to the intermediate 2 with all the necessary carbon atoms for the pheromone. Reductive removal of the SCO moiety in 2 followed by acetylation gave 1.

  （±）-黄色费洛蒙1已通过方案1中所示的路线合成。8元硫代碳酸酯4的[3,3]σ环膨胀专门产生了（Z）-10-元硫代碳酸酯3，将其转化通过三个步骤到达中间体2，该中间体2具有信息素的所有必需碳原子。在2中还原性去除SCO部分，然后进行乙酰化，得到1。
• Enantiodivergent route to both enantiomers of β-santalene and epi-β-santalene from a single chiral template
  作者：Seiichi Takano、Kohei Inomata、Ayako Kurotaki、Takehiko Ohkawa、Kunio Ogasawara

  DOI：10.1039/c39870001720

  日期：——

  An enantiodivergent route to both enantiomers of β-santalene and epi-β-santalene, constituents of East Indian sandalwood oil, has been developed using a single chiral template.

  以β檀香烯和两种对映体的enantiodivergent路线外延-β-檀香，东印度檀香精油的成分，一直采用单一手性模板开发。
• A convenient synthesis of [3-3H]squalene and [3-3H]-2,3-oxidosqualene
  作者：Maurizio Ceruti、Giorgio Grosa、Flavio Rocco、Franco Dosio、Luigi Cattel

  DOI：10.1002/jlcr.2580340613

  日期：1994.6

  [3-3H]Squalene and [3-3H]-2,3-oxidosqualene, key compounds for studying the biosynthesis of sterols, were synthesized. The main step was a modified Wittig reaction of [1-3H]trisnorsqualene aldehyde with a phosphorus ylide to give [3-3H]squalene or with a sulfur ylide to give [3-3H]-2,3-oxidosqualene. These compounds were obtained in high radiochemical yield and high purity under simple conditions.

  合成了[3-3H]角鲨烯和[3-3H]-2,3-氧化角鲨烯，它们是研究甾醇生物合成的关键化合物。主要步骤是[1-3H]三壬基喹啉醛与磷酰亚胺的改良维蒂希反应，得到[3-3H]角鲨烯，或与硫酰亚胺反应，得到[3-3H]-2,3-氧化角鲨烯。这些化合物在简单的条件下就能获得高放射化学收率和高纯度。
• Preparation and Photosensitized Oxidation of Isopropylidenecyclobutanes and -cyclobutenes
  作者：Aryeh A. Frimer、Joseph Weiss、Hugo E. Gottlieb、Joel L. Wolk

  DOI：10.1021/jo00083a019

  日期：1994.2

  Isopropylidenecyclobutanes 2-5 underwent facile ene reaction with singlet dioxygen, yielding (upon Ph(3)P reduction) the corresponding pairs of epimeric allylic alcohols 9 and 10, 11 and 12, 13 and 14, and 15 and 16, respectively. A combination of spectral evidence and molecular modeling studies were utilized in the structural assignment of the epimers. The data clearly indicate that steric considerations play an important role in determining the face of the ring which O-1(2) approaches. Isopropylidenecyclobutenes 6 and 7 reacted with singlet oxygen more slowly than their monoolefinic analogs, yielding upon reduction allylic alcohols 21b and 22, respectively. Benzo analog 7 also generated a small and solvent-dependent amount of isomeric aldehydes 23 and 24, presumably via a free-radical mechanism. n-Butyl diene 8 underwent rapid photosensitized oxygenation producing allylic alcohol 35 (as the O-1(2) ene product) and dione 37 (the Hock-cleavage product of allylic hydroperoxide 39, formed in turn via a free-radical route) in a 1:9 ratio. Ah initio (STO-3G) calculations confirm that, in their lowest energy conformations, compounds 2-8 are planar with the methylene ring hydrogens displaced ca. 36 degrees from the perpendicular. As a result, only exocyclic ene product is formed, since O-1(2) strongly prefers axial or pseudoaxial allylic hydrogens. These calculations combined with the relative rate data suggest that the initial interaction between the electrophilic O-1(2) and alkylidenecyclobutenes involves both ends of the singlet dioxygen molecule, in which the ''front'' end attacks the reactive exocyclic double bond while the ''back'' end obtains stabilization by interacting with the more electron rich but unreactive endocyclic olefin linkage. Because of this added, and presumably substantial, stabilization, the relative rates within this system are determined in part by the orbital coefficients at the latter olefinic center.