(1S,2R,5S)-2-isopropyl-5-methylcyclohexyl 2-diazo-2-phenylacetate | 161634-49-7

• 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: (1S,2R,5S)-2-isopropyl-5-methylcyclohexyl 2-diazo-2-phenylacetate
• 英文别名: (-)-menthyl phenyldiazoacetate；[(1S,2R,5S)-5-methyl-2-propan-2-ylcyclohexyl] 2-diazo-2-phenylacetate
• CAS: 161634-49-7
• 化学式: C₁₈H₂₄N₂O₂
• 分子量: 300.401
• InChiKey: FSNQCJYDIYLLQE-IMJJTQAJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.56
• 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：

  氨基甲酸甲酯 、 (1S,2R,5S)-2-isopropyl-5-methylcyclohexyl 2-diazo-2-phenylacetate 在 rhodium(II) acetate dimer 作用下， 以 二氯甲烷 为溶剂， 以68%的产率得到(1S,3S,4R)-3-Menthyl 2-methoxycarbonylamino-2-phenylacetate
  参考文献：
  名称：

  铑类胡萝卜素的NH插入反应。第1部分。α-氨基酸和α-氨基膦酸衍生物的制备

  摘要：

  在一定范围的N–H化合物存在下，乙酸铑（II）催化的重氮苯基乙酸酯1和3的分解导致中间类胡萝卜素的N–H插入反应并形成N-取代的苯基甘氨酸衍生物2和4。 α-二重氮苄基膦酸二甲酯5的反应构成了氨基膦酸酯6的简单路线。

  DOI：

  10.1039/p19960002879
• 作为产物：
  描述：

  D-薄荷醇 在 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (1S,2R,5S)-2-isopropyl-5-methylcyclohexyl 2-diazo-2-phenylacetate
  参考文献：
  名称：

  Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters

  摘要：

  A series of phenyldiazoacetates 3 derived from enantiomerically pure alcohols ((-)-borneol, (+)menthol, (-)-menthol, (-)-8-phenylmenthol, (-)-trans-2-phenylcyclohexanol, (+)-trans-2-phenyl-cyclohexanol, and (-)10-(dicyclohexylsulfamoyl)-D-isoborneol) were prepared from the corresponding alpha-keto esters 1 by way of the tosylhydrazones 2. Rhodium(II)-catalyzed decomposition of the diazoacetates 3 in the presence of water or alcohols resulted in carbenoid O-H insertion reactions to give the corresponding 2-hydroxy- or 2-alkoxyphenylacetates in good yield, but with varying degrees of diastereoselectivity. A range of rhodium(II) and other metal catalysts were investigated, with rhodium(II) acetate and rhodium(II) acetamide giving the best results. The stereochemistry of the major diastereomer was proved in most cases by independent synthesis from a mandelic acid derivative of known configuration. Possible mechanisms are discussed.

  DOI：

  10.1021/jo00119a023

文献信息

• Amination of Diazocarbonyl Compounds: N–H Insertion under Metal-Free Conditions
  作者：Xuesong Luo、Gui Chen、Lin He、Xueliang Huang

  DOI：10.1021/acs.joc.6b00233

  日期：2016.4.1

  Transition-metal-free intermolecular N–H insertion of α-diazocarbonyl compounds is reported. Among the series of nitrogen sources examined, dibenzenesulfonimide was found to be the choice in terms of the yields and the reaction time. Primary mechanistic experiments suggest that a pathway involving a sequence of protonation and nucleophilic substitution was preferred.

  据报道，无过渡金属的α-重氮羰基化合物的分子间NH插入。在所检查的一系列氮源中，发现二苯磺酰亚胺是产率和反应时间的选择。初步的机械实验表明，涉及质子化和亲核取代序列的途径是优选的。
• Visible-light-promoted selective <i>O</i>-alkylation of 2-pyridones with α-aryldiazoacetates
  作者：Jingya Yang、Ganggang Wang、Hongyan Zhou、Zhifeng Li、Ben Ma、Menghui Song、Rongxia Sun、Congde Huo

  DOI：10.1039/d0ob02350g

  日期：——

  A visible-light-promoted O–H insertion reaction between 2-pyridones and α-aryldiazoacetates has been developed. Upon visible light irradiation, the reaction proceeds smoothly under mild and catalyst-free conditions. A wide scope of 2-pyridones and α-aryldiazoacetates are well tolerated, and various O-alkylated 2-pyridones are obtained with perfect selectivity and good functional group tolerance. A

  在2-吡啶酮和α-芳基重氮乙酸酯之间的可见光促进了OH的插入反应。在可见光照射下，反应在温和且无催化剂的条件下平稳进行。广泛耐受2-吡啶酮和α-芳基重氮乙酸酯，并且以完美的选择性和良好的官能团耐受性获得了各种O-烷基化的2-吡啶酮。光诱导的自由基过程可能是出色的选择性的原因。
• Photochemical ring expansion reactions: synthesis of tetrahydrofuran derivatives and mechanism studies
  作者：Sripati Jana、Zhen Yang、Chao Pei、Xinfang Xu、Rene M. Koenigs

  DOI：10.1039/c9sc04069b

  日期：——

  of oxygen and sulfur ylide mediated rearrangements is even today a matter of debate. In this report, we describe ring expansion reactions of oxetane and thietane heterocycles that allow probing the underlying reaction mechanism under metal-free, photochemical conditions. This ring expansion proves highly efficient and allows the synthesis of tetrahydrofuran and thiolane heterocycles under mild and operationally

  氧和硫的内叶酸介导的重排的反应机理直到今天仍是一个辩论的问题。在这份报告中，我们描述了氧杂环丁烷和硫杂环丁烷杂环的扩环反应，这些反应可在无金属的光化学条件下探查潜在的反应机理。这种扩环被证明是高效的，并允许在温和且操作简单的反应条件下合成四氢呋喃和硫杂环戊烷杂环。这些研究揭示了氧或硫的硫化物的环膨胀的立体选择性方面的显着差异，对此进行了进一步的计算研究。DFT计算表明，羧基在叶立德形成下发生反应，相应的环扩环反应通过双自由基途径进行。
• Silver-mediated direct trifluoromethoxylation of α-diazo esters via the ⁻OCF₃ anion
  作者：Gao-Feng Zha、Jia-Bin Han、Xiao-Qian Hu、Hua-Li Qin、Wan-Yin Fang、Cheng-Pan Zhang

  DOI：10.1039/c6cc03040h

  日期：——

  Silver-mediated direct trifluoromethoxylation of α-diazo esters and ketosteroid was disclosed.

  银介导的α-重氮酯和酮类固醇的直接三氟甲氧基化反应被揭示。
• Rh-Catalyzed Chemoselective [4 + 1] Cycloaddition Reaction toward Diverse 4-Methyleneprolines
  作者：Wangshui Cai、Junxian Wu、Haowei Zhang、Hitesh B. Jalani、Guigen Li、Hongjian Lu

  DOI：10.1021/acs.joc.9b01466

  日期：2019.9.6

  An efficient synthesis of 4-methyleneproline derivatives has been developed through an Rh-catalyzed [4 + 1] cycloaddition strategy using 3-methyleneazetidines and diazo compounds. The reaction proceeds under very mild conditions with a high degree of chemoselectivity, and competing experiments revealed that it is the preferred reaction, dominant over the C–H insertion, O–H insertion, and olefin cyclopropanation

  通过使用3-亚甲基氮杂环丁烷和重氮化合物的Rh催化的[4 +1]环加成反应，已经开发了4-亚甲基脯氨酸衍生物的有效合成方法。该反应在非常温和的条件下进行，具有高度的化学选择性，竞争实验表明，它是优选的反应，优于在Rh卡宾化学中通常观察到的C–H插入，OH–H插入和烯烃环丙烷化反应。该方法可以将脯氨酸酯支架掺入药物和天然产物中。反应的分子内形式有效地提供了脯氨酸稠合的中小型三环杂环。克级反应，一次加入重氮化合物以及最小催化剂负载量为0.1 mol％进行得很顺利，这表明它们的实用性。