tert-butyl 1-naphthylacetate | 2122-69-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: tert-butyl 1-naphthylacetate
• 英文别名: tert-butyl 2-(naphthalen-1-yl)acetate；naphthalen-1-ylacetic acid tert-butyl ester；1,1-Dimethylethyl 1-naphthaleneacetate；tert-butyl 2-naphthalen-1-ylacetate
• CAS: 2122-69-2
• 化学式: C₁₆H₁₈O₂
• mdl: MFCD19543451
• 分子量: 242.318
• InChiKey: XZIRTOCXBMGKBS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.312
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  tert-butyl 1-naphthylacetate 在 copper(l) iodide 、 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 cesium fluoride 作用下， 以 N-甲基吡咯烷酮 、 乙腈 为溶剂， 反应 22.0h， 生成 tert-butyl 4,4,4-trifluoro-2-(naphthalen-1-yl)-3-(trifluoromethyl)but-2-enoate
  参考文献：
  名称：

  From C ₁ to C ₃ : Copper‐Catalyzed gem ‐Bis(trifluoromethyl)olefination of α‐Diazo Esters with TMSCF ₃

  摘要：

  AbstractA Cu‐catalyzed gem‐bis(trifluoromethyl)olefination of α‐diazo esters, using TMSCF3 as the only fluorocarbon source, has been developed and provides an exquisite method to access gem‐bis(trifluoromethyl)alkenes. This unprecedented olefination process involves a carbene migratory insertion into “CuCF3” to generate the α‐CF3‐substituted organocopper species, which then undergoes β‐fluoride elimination and two consecutive addition‐elimination processes to give the desired products. The key to this efficient one‐pot C1‐to‐C3 synthetic protocol lies in the controllable double (over single and triple) trifluoromethylations of the gem‐difluoroalkene intermediates.

  DOI：

  10.1002/anie.202002409
• 作为产物：
  描述：

  1-萘乙酸 在 吡啶 、 氯化亚砜 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 生成 tert-butyl 1-naphthylacetate
  参考文献：
  名称：

  peri-Dimethylamino substituent effects on proton transfer at carbon in α-naphthylacetateesters: a model for mandelate racemase

  摘要：

  在 1:â1 D2Oâ:âCD3CN 中的氘氧钾溶液中，测定了 8-(N,N-二甲基氨基萘-1-基)乙酸叔丁酯 1 和萘-1-基乙酸叔丁酯 2 δ-CH2位置上氢与氘交换的速率常数，以量化邻近的近二甲基氨基取代基对δ-质子化的影响。没有检测到邻近基团（弱碱性）对分子内一般碱催化作用的影响。酯 1 和酯 2 的氘交换反应的二阶速率常数 kDO 分别为 1.35 Ã 10â4 Mâ1 sâ1 和 3.95 Ã 10â3 Mâ1 sâ1 。引入一个近二甲基氨基后，kDO 值意外地降低了 29 倍，这是因为氘代氧化物离子对分子间去质子化作用产生了不利的立体和/或电子取代基效应。根据实验 kDO 值，计算出酯类 1 和 2 的碳酸 pKa 值分别为 26.8 和 23.1。

  DOI：

  10.1039/c1ob06525d

文献信息

• Synthesis of Rhodium Complexes with Chiral Diene Ligands via Diastereoselective Coordination and Their Application in the Asymmetric Insertion of Diazo Compounds into E−H Bonds
  作者：Nikita M. Ankudinov、Denis A. Chusov、Yulia V. Nelyubina、Dmitry S. Perekalin

  DOI：10.1002/anie.202105179

  日期：2021.8.16

  A new method for the synthesis of chiral diene rhodium catalysts is introduced. The readily available racemic tetrafluorobenzobarrelene complexes [(R2-TFB)RhCl]2 were separated into two enantiomers via selective coordination of one of them with the auxiliary S-salicyl-oxazoline ligand. One of the resulting chiral complexes with an exceptionally bulky diene ligand [(R,R-iPr2-TFB)RhCl]2 was an efficient

  介绍了一种合成手性二烯铑催化剂的新方法。容易获得的外消旋四氟苯并二甲苯配合物 [(R 2 -TFB)RhCl] 2通过其中之一与辅助S-水杨基-恶唑啉配体的选择性配位被分离成两种对映异构体。所得手性配合物之一具有异常庞大的二烯配体 [( R , R - i Pr 2 -TFB)RhCl] 2是重氮酯不对称插入 B-H 和 Si-H 键的有效催化剂，得到官能化的有机硼烷和硅烷具有高产率 (79–97 %) 和对映体纯度 (87–98 % ee）。通过 DFT 计算预测了辅助配体分离的立体选择性和催化反应的立体选择性。
• New methods and reagents in organic synthesis. 17. Trimethylsilyldiazomethane(TMSCHN2) as a stable and safe substitute for hazardous diazomethane. Its application to the arndt-eistert synthesis.
  作者：TOYOHIKO AOYAMA、TAKAYUKI SHIOIRI

  DOI：10.1248/cpb.29.3249

  日期：——

  Although diazomethane is used in the Arndt-Eistert synthesis, it is both highly toxic and also explosive, and hence should be very carefully handled. In place of this hazardous diazomethane, stable and safe trimethylsilyldiazomethane (TMSCHN2) was found to be very useful for the Arndt-Eistert synthesis. TMSCHN2 was easily acylated with a carboxylic acid chloride in tetrahydrofuran-acetonitrile, and thermal treatment of the acylated product in benzyl alcohol and 2, 4, 6-trimethylpyridine smoothly gave the benzyl ester of a homologated acid. Nucleophiles other than benzyl alcohol could also be used. TMSCHN2 may also be able to replace diazomethane in other areas of chemistry.

  尽管偶氮甲烷在阿恩特-艾斯特合成中使用，但它具有高毒性和爆炸性，因此应该非常小心地处理。为了替代这种危险的偶氮甲烷，稳定且安全的三甲基硅烷偶氮甲烷（TMSCHN₂）被发现对于阿恩特-艾斯特合成非常有用。TMSCHN₂可以在四氢呋喃-乙腈中与卤代羧酸酰氯轻松进行酰化，酰化产物在苄醇和2,4,6-三甲基吡啶中的热处理顺利得到了一种同 homologated acid 的苄酯。除了苄醇之外，其他亲核试剂也可以使用。TMSCHN₂可能还能够替代偶氮甲烷在其他化学领域的应用。
• Iron-catalyzed Chemoselective Cross-coupling of α-Bromocarboxylic Acid Derivatives with Aryl Grignard Reagents
  作者：Masayoshi Jin、Masaharu Nakamura

  DOI：10.1246/cl.2011.1012

  日期：2011.9.5

  We have developed a simple and effective synthetic method of α-arylcarboxylic acid derivatives based on the iron-catalyzed cross-coupling reaction of α-bromocarboxylic acid derivatives with aryl Grignard reagents. The reaction proceeds smoothly at −78 °C in a chemoselective manner to produce the coupling product in good to excellent yields.

  我们开发了一种基于铁催化α-溴代羧酸衍生物与芳基格氏试剂的交叉偶联反应的简单有效的α-芳基羧酸衍生物的合成方法。该反应在-78°C下能够选择性地顺利进行，以良好到优秀的收率得到偶联产物。
• One-pot borylation/Suzuki–Miyaura sp²–sp³ cross-coupling
  作者：Luke Whitaker、Hassan Y. Harb、Alexander P. Pulis

  DOI：10.1039/c7cc05037b

  日期：——

  One-pot borylation/Suzuki–Miyaura sp²–sp³ cross coupling allows efficient access to important diaryl methanes, allyl aryls and α-arylated carbonyl compounds.

  一锅硼化/铃木-宫浦sp²-sp³交叉偶联反应可以有效地合成重要的二芳基甲烷、烯丙芳基和α-芳基羰基化合物。
• Isotactic specific catalyst for direct production of highly isotactic poly (propylene oxide) or highly isotactic poly (butylene oxide)
  申请人：Coates Geoffrey W.

  公开号：US20080262164A1

  公开（公告）日：2008-10-23

  (Salph or methoxy salph) Co (initiating ligand) catalyze homopolymerizing rac-PO to produce pure highly isotactic PPO and rac-1-butylene oxide to produce pure isotactic poly(butylene oxide). A product is unfractionated isotactic PPO of m-dyad content >81%, normally at least 99%.

  （Salph或甲氧基Salph）Co（起始配体）催化同聚合物化的PO，产生纯度极高的异构PPO和异构聚丁烯氧化物。产物是未分级的异构PPO，m-双聚体含量>81%，通常至少为99%。