(1R,2S,5R)-menthol trifluoroacetate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R,2S,5R)-menthol trifluoroacetate
• 英文别名: (-)-menthyl 2,2,2-trifluoroacetate；(-)-menthyl trifluoroacetate；menthyl trifluoroacetate；[(1R,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl] 2,2,2-trifluoroacetate
• 化学式: C₁₂H₁₉F₃O₂
• 分子量: 252.277
• InChiKey: ATXCXBAHNZQECW-KXUCPTDWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.7
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1R,2S)-1-((1-(4-fluorophenyl)-1H-indazol-5-yl)oxy)-1-(3-methoxyphenyl)propan-2-amine 、 (1R,2S,5R)-menthol trifluoroacetate 在 lanthanide triflate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.33h， 生成
  参考文献：
  名称：

  Efficient DBU accelerated synthesis of ¹⁸F-labelled trifluoroacetamides

  摘要：

  溴二氟乙酰胺的亲核性¹⁸F-氟化反应在DBU存在下进行。提出了DBU作为有机中介的机理。

  DOI：

  10.1039/c6cc08535k
• 作为产物：
  描述：

  (1R,2S,5R)-2-isopropyl-5-methylcyclohexyl 2-bromo-2,2-difluoroacetate 在 C₅₄H₄₅CuFP₃ 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 以88%的产率得到(1R,2S,5R)-menthol trifluoroacetate
  参考文献：
  名称：

  晚期铜（I）介导的亲核氟化合成三氟甲基

  摘要：

  描述了由配合物（PPh 3）3 CuF介导的溴二氟甲基衍生物的亲核氟化。在反应条件下，以良好的产率获得了不同的三氟乙酸酯，三氟酮，三氟芳烃和三氟乙酰胺。

  DOI：

  10.1016/j.jfluchem.2016.12.017

文献信息

• Synthesis of Fluorinated Alkyl Aryl Ethers by Palladium-Catalyzed C–O Cross-Coupling
  作者：Robert Szpera、Patrick G. Isenegger、Maxime Ghosez、Natan J. W. Straathof、Rosa Cookson、David C. Blakemore、Paul Richardson、Véronique Gouverneur

  DOI：10.1021/acs.orglett.0c02347

  日期：2020.8.21

  cross-coupling of (hetero)aryl bromides with fluorinated alcohols using the commercially available precatalyst tBuBrettPhos Pd G3 and Cs2CO3 in toluene. This Pd-catalyzed coupling features a short reaction time, excellent functional group tolerance, and compatibility with electron-rich and -poor (hetero)arenes. The method provides access to 18F-labeled trifluoroethyl ethers by cross-coupling with [

  在本文中，我们报告了一种高效的方案，可使用市售的预催化剂t BuBrettPhos Pd G3和Cs 2 CO 3在甲苯中将（杂）芳基溴化物与氟化醇交叉偶联。这种钯催化的偶联反应具有反应时间短，对官能团的耐受性强以及与富电子和贫电子（杂）芳烃相容的特点。该方法通过与[ 18 F]三氟乙醇交叉偶联而获得18 F-标记的三氟乙基醚。
• Photoredox‐Catalyzed Defluorinative Functionalizations of Polyfluorinated Aliphatic Amides and Esters
  作者：Jian‐Heng Ye、Peter Bellotti、Corinna Heusel、Frank Glorius

  DOI：10.1002/anie.202115456

  日期：2022.2.21

  A new catalytic approach to selective functionalization of the strong C−F bonds in polyfluorinated aliphatic esters and amides is reported, affording a diverse array of important partially fluorinated motifs through hydrodefluorination, defluoroalkylation, and defluoroalkenylation. Straightforward downstream chemistry towards fluorinated alcohols, amines and drug derivatives highlights the potential

  报道了一种选择性功能化多氟脂肪族酯和酰胺中强 C-F 键的新催化方法，通过加氢脱氟、脱氟烷基化和脱氟烯基化提供多种重要的部分氟化基序。对氟化醇、胺和药物衍生物的直接下游化学突出了该协议的潜力。
• Solvent- and Base-Free Dicyclohexylcarbodiimide-Promoted Esterifications
  作者：Ludvík Streinz、Bohumír Koutek、David Šaman

  DOI：10.1055/s-2001-14605

  日期：——

  N,N′-Dicyclohexylcarbodiimide/base-promoted esterification of carboxylic acids containing α-halogen atom(s) gave low yields of products when performed in a solvent. This failure was found to be due to the low stability of appropriate intermediates under the reaction conditions. On the other hand, high yields of esters were obtained, when the same esterification was performed without both the solvent and base. Carboxylic acids without α-halogen atom(s) also undergo the esterification under solvent- and base-free conditions giving products in medium yield.

  N,N′-二环戊基碳二亚胺/碱催化的α-卤代羧酸酯化在溶剂中进行时产率较低。这一失败被发现是由于反应条件下适当中间体的稳定性较差。另一方面，当在无溶剂和无碱的条件下进行相同的酯化反应时，得到了高产率的酯。没有α-卤代原子的羧酸在无溶剂和无碱的条件下也能进行酯化反应，产物的产率为中等水平。
• Hypervalent Iodine-Based Activation of Triphenylphosphine for the Functionalization of Alcohols
  作者：Jasmin Eljo、Myriam Carle、Graham Murphy

  DOI：10.1055/s-0036-1589069

  日期：2017.12

  The use of hypervalent iodine reagents as a general tool for the activation of PPh3 and its application to the functionalization of alcohols is reported. Combination of PPh3 with PhICl2 or TolIF2 gives dihalophosphoranes that are characterized by 31P NMR, however, with PhIOAc2, PhI(OTFA)2, or the cyclic chloro(benzoyloxy)iodane, no phosphoranes were observed. Reaction of these iodanes with PPh3 in the presence of primary, secondary, or tertiary alcohols results in either halogenation or acyl-transfer products in moderate to high yield.

  报道了使用高价碘试剂作为活化PPh3的通用工具，并将其应用于醇的官能化。将PPh3与PhICl2或TolIF2结合得到二卤代膦烷，通过31P NMR进行表征，然而，与PhIOAc2、PhI(OTFA)2或环状氯代苯甲酰氧碘烷结合时，未观察到膦烷的形成。这些碘烷与PPh3在一次、二次或三次醇的存在下反应，产物为卤代化合物或酰基转移产物，产率中等至高。
• A selective and mild electrochemical defluorinative carboxylation for late-stage C(sp³)–F bond functionalization
  作者：Subhojit Mondal、Soumik Sarkar、Jason W. Wang、Michael W. Meanwell

  DOI：10.1039/d3gc03387b

  日期：——

  defluorinative carboxylation of trifluoromethyl (hetero)arenes, and trifluoromethyl-acetates and -acetamides, for accessing their highly valuable α,α-difluorocarboxylic acid analogues. Given the immense synthetic versatility of carboxylic acids, our new protocol may become a useful tool for accessing novel fluorinated analogues in drug design and agrochemical development.

  我们报告了三氟甲基（杂）芳烃、三氟甲基乙酸酯和三氟乙酰胺的电化学脱氟羧化的第一个通用方案，以获取其高价值的α,α-二氟羧酸类似物。鉴于羧酸的巨大合成多功能性，我们的新方案可能成为在药物设计和农用化学品开发中获取新型氟化类似物的有用工具。