D,L(rac)-menthyl diazoacetate

• 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: D,L(rac)-menthyl diazoacetate
• 英文别名: 2-isopropyl-5-methylcyclohexyl 2-diazoacetate；Diazoessigsaeure-1-menthylester；Diazoacetic acid, 2-isopropyl-5-methylcyclohexyl ester；(5-methyl-2-propan-2-ylcyclohexyl) (2E)-2-diazoacetate
• 化学式: C₁₂H₂₀N₂O₂
• 分子量: 224.303
• InChiKey: ARIRLMOIPLAKEK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  28.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  [platinum(II)dichloride(1,2-bis(diphenylphosphino)ethane)] 、 D,L(rac)-menthyl diazoacetate 以 氘代氯仿 为溶剂， 生成
  参考文献：
  名称：

  非对映选择性卡宾插入铂-卤素键中。[PtCl（R-CHClCO2Et）（R，R-diop）的晶体结构

  摘要：

  Ethyl diazoacetate reacts with [PtX2L2] [X = Cl, Br, 1; L2 = 1,5-cyclooctadiene (cod), 2 PPh3, Ph2P-(CH2)nPPh2, n = 1 (dppm), 2 (dppe), 3 (dppp), 4 (dppb)] to give the corresponding [PtX(CHXCO2Et)L2] as a racemic mixture in high yields. The cod ligands in [PtX(CHXCO2Et)(cod)] are readily displaced by PPh3 or diphosphines. When optically active complexes [PtX2L*] (X = Cl, I; L* = R,R-diop, S,S-chiraphos, S,S-skewphos) were treated with ethyl diazoacetate, the products (PtX(CHXCO2Et)L*] were mixtures of diastereoisomers in different proportions. The major diastereoisomer of [PtCl(CHClCO2Et)(R,R-diop)] was readily separated by fractional crystallization, and its crystal structure revealed that the configuration at the alpha-carbon was R. This compound is configurationally stable for at least 14 d in CDCl3 solution as shown by P-31 NMR spectroscopy. Treatment of pure [PtCl(CHClCO2Et)(R,R-diop)] with S,S-skewphos led to exchange of diphosphines and thereby the assignment of the S configuration at the alpha-carbon of the major product of the reaction of [PtCl2(S,S-skewphos)] with ethyl diazoacetate. With the aim of optimizing the diastereoselectivity of the insertion reaction, the chiral diazo ester N2CHCO2R (R = R,R-menthyl) was used as the reagent but it was found that the diastereoselectivities were similar to those with N2CHCO2Et. The highest diastereoselectivities (up to 7:1) were obtained with N2CHCOPh.

  DOI：

  10.1021/om00059a062
• 作为产物：
  描述：

  (5-Methyl-2-propan-2-ylcyclohexyl) 2-diazo-3-oxobutanoate 在 potassium hydroxide 作用下， 以 水 、 乙腈 为溶剂， 生成 D,L(rac)-menthyl diazoacetate
  参考文献：
  名称：

  重氮化合物与二硒化物和亲核试剂的电化学氧化双官能化

  摘要：

  已经开发出重氮化合物与二硒化物和亲核试剂的电化学氧化双官能化。这种创新方法产生了多种含硒吡唑酯和烷氧基酯，克服了传统合成方法的局限性。值得注意的是，各种亲核试剂，包括酸、醇和吡唑，都可以无缝结合。值得注意的是，该协议具有高原子效率、优异的官能团耐受性和良好的效率，并且在无过渡金属和氧化剂的条件下运行，在该领域脱颖而出。

  DOI：

  10.1021/acs.orglett.4c01074

文献信息

• ASYMMETRIC CYCLOPROPANATION OF ELECTRON-DEFICIENT OLEFINS WITH DIAZO REAGENTS
  申请人：Zhang X. Peter

  公开号：US20100076239A1

  公开（公告）日：2010-03-25

  Cobalt-catalyzed asymmetric cyclopropanation of electron-deficient olefins.

  钴催化的电子不足烯烃不对称环丙烷化。
• Copper(I)-Catalysed Domino Coupling and Cyclisation Reaction: A Mild, Expedient Route for the Synthesis of Indene and Dihydronaphthalene Derivatives
  作者：Gullapalli Kumaraswamy、Guniganti Balakishan

  DOI：10.1002/ejoc.201500284

  日期：2015.5

  A substoichiometric copper iodide catalysed synthesis of indene and dihydronaphthalene derivatives has been accomplished. This protocol is compatible with functional groups, and results in various scaffolds of indene and dihydronaphthalene derivatives in good to high yields. By employing this protocol, a functionalised cyclohexenone derivative is also achieved.

  已经完成了亚化学计量的碘化铜催化合成茚和二氢萘衍生物。该协议与官能团兼容，并导致茚和二氢萘衍生物的各种支架以良好到高产率。通过使用该协议，还实现了功能化的环己烯酮衍生物。
• Synthesis of Substituted Pyrazoles via Tandem Cross-Coupling/Electrocyclization of Enol Triflates and Diazoacetates
  作者：David J. Babinski、Hector R. Aguilar、Raymond Still、Doug E. Frantz

  DOI：10.1021/jo201042c

  日期：2011.8.5

  The synthesis of 3,4,5-trisubstituted pyrazoles via a tandem catalytic cross-coupling/electrocyclization of enol triflates and diazoacetates is presented. The initial scope of this methodology is demonstrated on a range of differentially substituted acyclic and cyclic enol triflates as well as an elaborated set of diazoacetates to provide the corresponding pyrazoles with a high degree of structural

  介绍了通过烯醇三氟甲磺酸酯和重氮乙酸酯的串联催化交叉偶联/电环化合成 3,4,5-三取代的吡唑。该方法的初始范围在一系列差异取代的无环和环状烯醇三氟甲磺酸酯以及一组精心设计的重氮乙酸酯上得到证明，以提供具有高度结构复杂性的相应吡唑。
• Chiral rhodium(II) carboxamides. A new class of catalysts for enantioselective cyclopropanation reactions
  作者：Michael P. Doyle、Bridget D. Brandes、Amy P. Kazala、Roland J. Pieters、Michael B. Jarstfer、Linette M. Watkins、Cassandra T. Eagle

  DOI：10.1016/s0040-4039(00)97128-4

  日期：1990.1

  Chiral Rh2L4 (L = 4-substituted-oxazolidinones and methyl 2-pyrrolidone-5-carboxylate) having two nitrogen-rhodium bonds in the cis geometry at each rhodium face are effective catalysts for enantioselective intermolecular cyclopropanation reactions.

  在每个铑面的顺式几何结构中具有两个氮-铑键的手性Rh 2 L 4（L = 4-取代的恶唑烷酮和2-吡咯烷酮-5-羧酸甲酯）是对映选择性分子间环丙烷化反应的有效催化剂。
• A new class of bis-oxazoline ligands for the Cu-catalysed asymmetric cyclopropanation of olefins
  作者：Ashutosh V. Bedekar、Pher G. Andersson

  DOI：10.1016/0040-4039(96)00736-8

  日期：1996.6

  A set of new chiral bis-oxazolines, 5a-b and 6a-c, has been syntheised from D and L-diethyl 2,3-O-isopropylidene tartrates and chiral amino alcohols. These ligands were found to be efficient in the Cu(I)-catalysed asymmetric cyclopropanation of olefins. Bis-oxazolines of this type based on readily available valine were found comparable with previous ligands based on the more expensive tert-leucine

  由D和L-二乙基2，3- O-异亚丙基酒石酸酯和手性氨基醇合成了一组新的手性双-恶唑啉5a-b和6a-c。发现这些配体在Cu（I）催化的烯烃的不对称环丙烷化中是有效的。发现基于易得的缬氨酸的这种类型的双恶唑啉与先前的基于较昂贵的叔亮氨酸的配体相当。