(-)-(1R,3R,4S)-8-phenylmenthyl 2-diazo-2-phenylacetate | 161634-63-5

• 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,3R,4S)-8-phenylmenthyl 2-diazo-2-phenylacetate
• 英文别名: 8-Phenyl-3-menthyl 2-diazo-2-phenylacetate；(1R,2S,5R)-8-Phenylmenthyl 2-diazophenylacetate；(1R,2S,5R)-8-phenylmenthyl 2-diazo-2-phenylacetate；phenylmenthyl phenyldiazoacetate；[(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] 2-diazo-2-phenylacetate
• CAS: 161634-63-5
• 化学式: C₂₄H₂₈N₂O₂
• 分子量: 376.499
• InChiKey: MRQJIIRNNUCAEM-DUXKGJEZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  28
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 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：

  (-)-(1R,3R,4S)-8-phenylmenthyl 2-diazo-2-phenylacetate 在 rhodium(II) acetate dimer 水 、 silver(l) oxide 作用下， 以 二氯甲烷 为溶剂， 反应 30.0h， 生成 (1R,3R,4S)-8-phenylmenthyl (R)-2-isopropoxy-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
• 作为产物：
  描述：

  (-)-8-苯基薄荷醇 在 对甲苯磺酸 、 三乙胺 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 生成 (-)-(1R,3R,4S)-8-phenylmenthyl 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

• Palladium-catalyzed carbenoid based N–H bond insertions: application to the synthesis of chiral α-amino esters
  作者：Gang Liu、Jian Li、Lin Qiu、Li Liu、Guangyang Xu、Bing Ma、Jiangtao Sun

  DOI：10.1039/c3ob41331d

  日期：——

  A highly efficient palladium-catalyzed carbenoid based N–H bond insertion has been developed. The α-amino esters were obtained in high isolated yields. Moreover, by choosing a suitable chiral auxiliary, stereoselective Pd-catalyzed N–H insertion has been realized. The chiral α-amino esters were obtained in high yields (up to 91%) and with excellent diastereoselectivities (d.r. > 19 : 1).

  开发了一种高效的钯催化基于卡宾的N–H键插入反应。得到了高产率的α-氨基酸酯。此外，通过选择合适的立体辅助剂，实现了立体选择性的Pd催化N–H插入反应。得到了高产率（高达91%）和优异的非对映选择性（d.r. > 19:1）的手性α-氨基酸酯。
• N–H insertion reactions of rhodium carbenoids. Part 1. Preparation of α-amino acid and α-aminophosphonic acid derivatives
  作者：Enrique Aller、Richard T. Buck、Martin J. Drysdale、Leigh Ferris、David Haigh、Christopher J. Moody、Neil D. Pearson、J. Bobby Sanghera

  DOI：10.1039/p19960002879

  日期：——

  Rhodium(II) acetate-catalysed decomposition of diazophenylacetates 1 and 3 in the presence of a range of N–H compounds results in an N–H insertion reaction of the intermediate carbenoids and formation of N-substituted phenylglycine derivatives 2 and 4. The corresponding reactions of dimethyl α-diazobenzylphosphonate 5 constitute a simple route to aminophosphonates 6.

  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。
• Copper-catalyzed annulation of α-substituted diazoacetates with 2-ethynylanilines: the direct synthesis of C2-functionalized indoles
  作者：Gang Liu、Guangyang Xu、Jian Li、Dong Ding、Jiangtao Sun

  DOI：10.1039/c3ob42350f

  日期：——

  Copper-catalyzed direct annulation of α-substituted diazoacetates with 2-ethynylanilines leading to C2-functionalized indoles was achieved under mild reaction conditions. The C2-(carboxylate methyl) substituted indoles were obtained in moderate to high yields. In addition, this procedure tolerates a series of N-substituted and free substituted 2-ethynylanilines.

  在温和的反应条件下，铜催化的α-取代的重氮乙酸酯与2-乙炔基苯胺的直接环化反应，生成了C2官能化的吲哚。C2-（羧甲基）吲哚以中等至高收率获得。另外，该方法耐受一系列N-取代的和自由取代的2-乙炔基苯胺。
• Rhodium(I)-Catalyzed Sequential C(sp)C(sp³) and C(sp³)C(sp³) Bond Formation through Migratory Carbene Insertion
  作者：Ying Xia、Sheng Feng、Zhen Liu、Yan Zhang、Jianbo Wang

  DOI：10.1002/anie.201503140

  日期：2015.6.26

  A RhI‐catalyzed three‐component reaction of tert‐propargyl alcohol, diazoester, and alkyl halide has been developed. This reaction can be considered as a carbene‐involving sequential alkyl and alkynyl coupling, in which C(sp)C(sp3) and C(sp3)C(sp3) bonds are built successively on the carbenic carbon atom. The RhI‐carbene migratory insertion of an alkynyl moiety and subsequent alkylation are proposed

  已开发出一种Rh I催化的叔炔丙醇，重氮酸酯和烷基卤的三组分反应。该反应可视为涉及卡宾的顺序烷基和炔基偶合，其中C（sp）C（sp 3）和C（sp 3）C（sp 3）键是在羧基碳原子上连续建立的。提出了Rh I-卡宾迁移插入炔基部分和随后进行烷基化的方法，以解释两个独立的CC键形成。该反应为全碳四元中心的构建提供了一种有效且可调节的方法。
• Diastereoselectivity in the O - H Insertion Reactions of Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. II. Comparison of Rhodium(II)- and Acid-Mediated Reactions
  作者：David J. Miller、Christopher J. Moody、C. Neil Morffitt

  DOI：10.1071/c98159

  日期：——

  Rhodium(II)- or acid-mediated decomposition of 2-diazo-2-phenylacetates of chiral alcohols in the presence of various hydroxylic compounds (ROH) results in the diastereoselective formation of 2- hydroxy-, 2-alkoxy- or 2-trialkylsiloxy-2-phenylacetates, with the acid-mediated process giving the higher diastereoselectivity.

  铑（II）或酸介导的手性醇的 2-重氮-2-苯基乙酸酯的分解 手性醇的 2-重氮-2-苯基乙酸酯在各种羟基化合物 (ROH) 存在下进行分解，结果是 非对映选择性地形成 2-羟基、2-烷氧基或 2-三烷基硅氧基-2-苯基乙酸酯的非对映选择性，其中以酸为介导的过程具有较高的非对映选择性。 非对映选择性更高。