Bornyl 2-diazo-2-phenylacetate | 161634-62-4

• 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: Bornyl 2-diazo-2-phenylacetate
• 英文别名: <(1S)-endo>-Bornyl 2-diazophenylacetate；(1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 2-diazo-2-phenylacetate；[(1S,2R,4S)-1,7,7-trimethyl-2-bicyclo[2.2.1]heptanyl] 2-diazo-2-phenylacetate
• CAS: 161634-62-4
• 化学式: C₁₈H₂₂N₂O₂
• 分子量: 298.385
• InChiKey: JTXWLJRGLCESOA-PMUMKWKESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  22
• 可旋转键数：
  4
• 环数：
  3.0
• 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：

  Bornyl 2-diazo-2-phenylacetate 在 pyridine hydrofluoride 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 以99%的产率得到(1S,2R,4S)-1,7,7-trimethylbicyclo[2.2.1]heptan-2-yl 2-fluoro-2-phenylacetate
  参考文献：
  名称：

  H-F 键插入 α-重氮羰基化合物

  摘要：

  报道了将 H-F 键插入 α-重氮羰基化合物的反应。该协议描述了一个简单的反应设置，使用市售的 HF·pyr（Olah 试剂）作为氟源。该方法快速实用，并且可以以通常良好的收率获得广泛的 α-氟化羰基化合物。

  DOI：

  10.1039/d2ob00400c
• 作为产物：
  描述：

  <(1S)-endo>-Bornyl 2-oxophenylacetate tosylhydrazone 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 以98%的产率得到Bornyl 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

• 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。
• 10.1021/acscatal.4c03569
  作者：Kadam, Ganesh Arjun、Singha, Tushar、Rawat, Sapna、Hari, Durga Prasad

  DOI：10.1021/acscatal.4c03569

  日期：——

  Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates in diverse chemical synthesis. Despite this, the regioselective and stereoselective synthesis of skipped dienes remains a challenging goal. Strain release in organic molecules is a powerful tool for creating chemical complexity under mild conditions. The reactivity of

  跳过二烯不仅存在于脂肪酸初级代谢物和天然产物中，而且还作为多种化学合成中的反应中间体。尽管如此，跳跃二烯的区域选择性和立体选择性合成仍然是一个具有挑战性的目标。有机分子中的应变释放是在温和条件下创造化学复杂性的强大工具。应变双环[1.1.0]丁烷（BCB）系统的反应性主要由依赖于其固有亲电反应性的转化主导。在此，我们报告了基于铑-卡宾化学的BCB系统的卡宾型反应性的罕见例子，该系统能够通过应变释放高度立体选择性地合成跳跃二烯。该反应与重氮化合物和BCB上的各种官能团兼容，并且可以成功应用于复杂结构，提供高价值且可官能化的跳跃二烯。反应过程中引入的官能团充当下游操作的合成手柄。观察到的高立体选择性已基于 DFT 计算合理化，这表明反应可能通过协调机制进行，金属卡宾和 BCB 之间的非共价相互作用主要控制观察到的排他选择性。
• Diastereoselectivity in the OH insertion reactions of rhodium carbenoids derived from phenyldiazoacetates of homochiral alcohols
  作者：Enrique Aller、Geoffrey G. Cox、David J. Miller、Christopher J. Moody

  DOI：10.1016/s0040-4039(00)78227-x

  日期：1994.8

  Rhodium(II) acetate catalysed decomposition of the phenyldiazoacetates 3 in the presence of alcohols (methanol, propan-2-ol, tert-butanol) led to the O-II insertion products 4-6 in varying yields; the diastercomeric excess of the product ranged from 5-53%.
• Diastereoselectivity in the O-H Insertion Reactions of Rhodium Carbenoids Derived from Phenyldiazoacetates of Chiral Alcohols. Preparation of .alpha.-Hydroxy and .alpha.-Alkoxy Esters
  作者：Enrique Aller、David S. Brown、Geoffrey G. Cox、David J. Miller、Christopher J. Moody

  DOI：10.1021/jo00119a023

  日期：1995.7

  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.
• H–F bond insertions into α-diazo carbonyl compounds
  作者：Laiéli S. Munaretto、Rafael D. C. Gallo、Luiz Paulo M. O. Leão、Igor D. Jurberg

  DOI：10.1039/d2ob00400c

  日期：——

  A reaction for H–F bond insertion into α-diazo carbonyl compounds is reported. The protocol describes a simple reaction setup employing commercially available HF·pyr (Olah reagent) as the fluorine source. The method is rapid and practical, and allows access to a broad range of α-fluorinated carbonyl compounds in generally good yields.

  报道了将 H-F 键插入 α-重氮羰基化合物的反应。该协议描述了一个简单的反应设置，使用市售的 HF·pyr（Olah 试剂）作为氟源。该方法快速实用，并且可以以通常良好的收率获得广泛的 α-氟化羰基化合物。