(3R)-3-(4,4-dimethyl-2-oxotetrahydrofuranyl) (E)-2-diazo-4-phenyl-3-butenoate | 153062-67-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3R)-3-(4,4-dimethyl-2-oxotetrahydrofuranyl) (E)-2-diazo-4-phenyl-3-butenoate
• 英文别名: [(3R)-4,4-dimethyl-2-oxooxolan-3-yl] (E)-2-diazo-4-phenylbut-3-enoate
• CAS: 153062-67-0
• 化学式: C₁₆H₁₆N₂O₄
• 分子量: 300.314
• InChiKey: FQDYHRXRDKCJMB-XEHSLEBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3R)-3-(4,4-dimethyl-2-oxotetrahydrofuranyl) (E)-2-diazo-4-phenyl-3-butenoate 在 rhodium(II) acetate dimer 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 12.5h， 生成 methyl (1R,2R)-2-phenyl-1-[(E)-2-phenylvinyl]cyclopropanecarboxylate
  参考文献：
  名称：

  Davies, Huw M. L.; Huby, Nicholas J. S.; Cantrell Jr., William R., Journal of the American Chemical Society, 1993, vol. 115, # 21, p. 9468 - 9479

  摘要：

  DOI：
• 作为产物：
  描述：

  (3R)-3-(4,4-dimethyl-2-oxotetrahydrofuranyl) (E)-4-phenyl-3-butenoate 在 ABSA 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 0.5h， 生成 (3R)-3-(4,4-dimethyl-2-oxotetrahydrofuranyl) (E)-2-diazo-4-phenyl-3-butenoate
  参考文献：
  名称：

  A Stereospecific Access to Allylic Systems Using Rhodium(II)−Vinyl Carbenoid Insertion into Si−H, O−H, and N−H Bonds

  摘要：

  Rhodium-catalyzed decomposition of alpha-vinyldiazoesters in the presence of silanes, alcohols, ethers, amines, and thiols have been shown to produce the corresponding alpha-silyl, alpha-hydroxy, alpha-alkoxy, alpha-amino, and alpha-thioalkoxy esters in generally good yield with a complete retention of the stereochemistry of the double bond of the diazo precursor. An extension of the process in homochiral series has also been devised using either a chiral auxiliary attached to the ester function or achiral alpha-vinyldiazoesters and Doyle's chiral catalyst Rh-2(MEPY)(4). In the former approach, pantolactone as chiral auxiliary gave diastereoselectivities of up to 70%, while the second approach produced the desired allylsilane with ee as high as 72%. On the other hand, Rh-2(MEPY)(4)-catalyzed insertion into the O-H bond of water led to poor or no enantioselectivity in good agreement with recent literature reports.

  DOI：

  10.1021/jo961952j

文献信息

• Rhodium(II)-vinylcarbenoid insertion into the SiH bond. A new stereospecific synthesis of allylsilanes
  作者：Yannick Landais、Denis Planchenault、Valéry Weber

  DOI：10.1016/0040-4039(94)88508-7

  日期：1994.12

  catalysed decomposition of vinyldiazocarbonyl compounds in the presence of organosilanes led stereospecifically to the corresponding allylsilanes in good yields. An asymmetric approach has also been considered as well as the extension of the methodology to the synthesis of other allylic systems.

  在有机硅烷的存在下，Rh 2（OAc）4催化的乙烯基重氮羰基化合物的分解立体定向地以良好的收率生成了相应的烯丙基硅烷。还考虑了不对称方法，以及将方法扩展到其他烯丙基系统的合成。
• α-hydroxy esters as inexpensive chiral auxiliaries in rhodium(II)-catalyzed cyclopropanations with vinyldiazomethanes
  作者：Huw M.L. Davies、William R. Cantrell

  DOI：10.1016/0040-4039(91)80206-l

  日期：1991.11

  High levels of asymmetric induction were achieved in rhodium(II) catalyzed cyclopropanations with chiral vinyldiazomethanes. (R)-(−)-Pantolactone is the most effective chiral auxiliary, but other α-hydroxy esters also give reasonable levels of diastereoselectivity.

  在铑（II）与手性乙烯基重氮甲烷催化的环丙烷化反应中实现了高水平的不对称诱导。（R）-（-）-戊内酯是最有效的手性助剂，但其他α-羟基酯也可提供合理水平的非对映选择性。
• Chiral catalyst enhancement of diastereocontrol for OH insertion reactions of styryl- and phenyldiazoacetate esters of pantolactone
  作者：Michael P. Doyle、Ming Yan

  DOI：10.1016/s0040-4039(02)01282-0

  日期：2002.8

  The chiral dirhodium(II) catalyst Rh2(MEAZ)4 increases diastereocontrol for intermolecular OH insertion reactions of diazo esters having a chiral auxiliary over that achieved with Rh2(OAc)4.

  手性dirhodium（II）催化剂Rh 2（MEAZ）4与Rh 2（OAc）4相比，提高了对具有手性助剂的重氮酯的分子间O insertionH插入反应的非对映控制。