<1-(2H3)methyl(2-2H3)ethyl>triphenylphosphonium bromide | 127208-25-7

• 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: <1-(2H3)methyl(2-2H3)ethyl>triphenylphosphonium bromide
• 英文别名: 1,1,1,3,3,3-hexadeuterio-2-propyltriphenylphosphonium bromide
• CAS: 127208-25-7
• 化学式: Br*C₂₁H₂₂P
• 分子量: 391.236
• InChiKey: HSOZCYIMJQTYEX-TXHXQZCNSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  1.39
• 重原子数：
  23.0
• 可旋转键数：
  6.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  <1-(2H3)methyl(2-2H3)ethyl>triphenylphosphonium bromide 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 4.0h， 生成 triphenylphosphoranylidene-isopropane-d6
  参考文献：
  名称：

  Braverman, Samuel; Duar, Ytzhak, Journal of the American Chemical Society, 1990, vol. 112, # 15, p. 5830 - 5837

  摘要：

  DOI：
• 作为产物：
  描述：

  2-溴丙烷-D6 、 三苯基膦 反应 48.0h， 以36%的产率得到<1-(2H3)methyl(2-2H3)ethyl>triphenylphosphonium bromide
  参考文献：
  名称：

  Regiospecificity and isotope effects associated with the methyl-methylene eliminations in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene

  摘要：

  [8-H-3]-, [8,8,9,9-H-2(4)]-, and [1-H-3,8,9-H-2(6)] geranyl diphosphates (1-t, 1-d4, and 1-d6,t) were synthesized and used as substrates for several monoterpene cyclases to determine the regiospecificity and isotope effects attending the terminating proton transfers in the enzyme-catalyzed biosynthesis of (R)- and (S)-limonene. Degradation of enantiomeric [H-3]limonenes produced by cyclization Of 1-t with the (+)- and (-)-pinene cyclases (synthases) from Salvia officinalis demonstrated that the eliminations occur at both the cis- (55-65%) and trans-methyl (45-35%) groups. In contrast, the terminating eliminations in the formation of (+)- and (-)-limonene catalyzed by limonene cyclasses from Citrus sinensis and Perilla frutescens, respectively, were shown by degradation to occur exclusively (greater-than-or-equal-to 97-98%) at the cis terminal methyl group. The intramolecular isotope effects for the methyl-methylene elimination in limonene biosynthesis catalyzed by (+)- and (-)-pinene cyclases from S. officinalis were found to be k(H)/k(D) = 2.3 +/- 0.2 and 5.9 +/- 0.5, respectively, by GC/MS determinations of [H-2]-limonene derived from enzymatic cyclizations of 1-d4. Similar experiments with (-)-limonene cyclase from Mentha spicata resulted in k(H)/k(D) = 4.0 +/- 0.4. Incubations of 1-d6,t with pinene and bornyl PP cyclases from S. officinalis exhibited significant remote isotope effects (k(H)/k(D) = 1.16-1.27) on the total rate of monoterpene formation which suggest that the initial cyclization step of the enzyme-bound linalyl diphosphate intermediate is an important component of the overall rate of the enzymatic reactions. The isotope effects on the partitioning of the alpha-terpinyl carbocation intermediate between bicyclization and elimination to limonene were determined from the effects of deuterium substitution on the product ratios derived from enzymatic cyclization of 1-d6,t. The small size of these product isotope effects (k(H)/k(D)) = 1.2-1.7) is attributed to a conformational inversion of the alpha-terpinyl ion to a half-chair conformer prior to proton elimination to limonene, thereby rendering the bicyclizations relatively immune to the intrinsic deuterium isotope effect. The regiospecific proton transfers from the cis terminal methyl group effected by the limonene cyclases from Citrus and Perilla are attributed to the minimization of charge separation in the transition state.

  DOI：

  10.1021/jo00067a037

文献信息

• Manganese(I)-Catalyzed Synthesis of Fused Eight- and Four-Membered Carbocycles via C–H Activation and Pericyclic Reactions
  作者：Youwei Xu、Guangfan Zheng、Lingheng Kong、Xingwei Li

  DOI：10.1021/acs.orglett.9b01139

  日期：2019.5.3

  facile construction of complex cycles. On the other hand, metal-catalyzed C–H activation has been established as an important strategy for rapid synthesis of complex structures. The two areas are integrated in Mn(I)-catalyzed redox-neutral coupling of 3-alkenyl- and 3-allylindoles with propargylic carbonates, which occurred via C–H allenylation with subsequent pericyclic reactions to afford fused eight-

  周环反应使得可以容易地构建复杂的循环。另一方面，金属催化的C–H活化已被确立为快速合成复杂结构的重要策略。这两个区域都整合在了Mn（I）催化的3-烯基和3-烯丙醇的氧化还原-中性偶合与炔丙基碳酸酯中，这是通过C-H烯基化和随后的周环反应发生的，从而得到稠合的八元和四元碳环， 分别。
• Mass spectrometry in structural and stereochemical problems. CCXVIII. Electron impact induced behavior of terpenoid esters of the juvenile hormone class
  作者：Raymond J. Liedtke、Carl Djerassi

  DOI：10.1021/jo00978a012

  日期：1972.6