[(2S,3S,5S,6S)-5,6-diethoxy-5,6-dimethyl-3-[[(E)-3-phenylprop-2-enoyl]oxymethyl]-1,4-dioxan-2-yl]methyl (E)-3-phenylprop-2-enoate | 181785-10-4

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: [(2S,3S,5S,6S)-5,6-diethoxy-5,6-dimethyl-3-[[(E)-3-phenylprop-2-enoyl]oxymethyl]-1,4-dioxan-2-yl]methyl (E)-3-phenylprop-2-enoate
• CAS: 181785-10-4
• 化学式: C₃₀H₃₆O₈
• 分子量: 524.611
• InChiKey: NHUQGZVVMMHLAO-FVKPRKMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  38
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  [(2S,3S,5S,6S)-5,6-diethoxy-5,6-dimethyl-3-[[(E)-3-phenylprop-2-enoyl]oxymethyl]-1,4-dioxan-2-yl]methyl (E)-3-phenylprop-2-enoate 以 甲苯 为溶剂， 反应 60.0h， 生成 (1S,5R,6S,7R,8R,12S,14S,15S)-14,15-Diethoxy-14,15-dimethyl-6,7-diphenyl-3,10,13,16-tetraoxa-tricyclo[10.4.0.0^5,8]hexadecane-4,9-dione 、 (1S,5R,6S,7S,8R,12S,14S,15S)-14,15-Diethoxy-14,15-dimethyl-6,7-diphenyl-3,10,13,16-tetraoxa-tricyclo[10.4.0.0^5,8]hexadecane-4,9-dione 、 (1S,5R,6S,7R,8S,12S,14S,15S)-14,15-Diethoxy-14,15-dimethyl-6,7-diphenyl-3,10,13,16-tetraoxa-tricyclo[10.4.0.0^5,8]hexadecane-4,9-dione 、 (1S,5S,6R,7R,8S,12S,14S,15S)-14,15-Diethoxy-14,15-dimethyl-6,7-diphenyl-3,10,13,16-tetraoxa-tricyclo[10.4.0.0^5,8]hexadecane-4,9-dione
  参考文献：
  名称：

  Investigations of the Asymmetric Intramolecular [2 + 2] Photocycloaddition and Its Application as a Simple Access to Novel C₂-Symmetric Chelating Bisphosphanes Bearing a Cyclobutane Backbone

  摘要：

  The asymmetric intramolecular [2 + 2] photocycloaddition of alpha,beta-enoates was evaluated as a simple access to the novel Ct-symmetric bisphosphanes 22 and 27 possessing a cyclobutane backbone. A source of different chiral auxiliaries for investigations of the photochemical key step was provided by the transacetalization of dialkyl tartrates 3 with the corresponding 3,3-dialkoxybutan-2-ones 4. An insight into the selection mechanism was gained by temperature dependent measurements on the irradiation of the dicinnamates 10a-d, since the corresponding Eyring diagram discloses strictly linear functions as well as an isoselective relationship. Diol 8a turned out to be a structurally optimized auxiliary in terms of chiral induction and product crystallization and was also successfully applied in the first asymmetric photodimerization of 2-indenecarboxylic acid esters. Indeed, in this case excellent diastereoselectivities were achieved, too, but head-to-tail dimers 16a and 16b were formed predominantly. Diesters 11a and 16a were converted by standard procedures into the desired enantiopure 1,4-diphosphane 22 and 1,5-diphosphane 27. Furthermore, the hitherto unknown absolute configuration of delta-truxinic acid was elucidated from a single crystal X-ray structure analysis of 11a.

  DOI：

  10.1021/jo960556y
• 作为产物：
  描述：

  (2R,3R)-5,6-Diethoxy-5,6-dimethyl-[1,4]dioxane-2,3-dicarboxylic acid diethyl ester 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 吡啶 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 [(2S,3S,5S,6S)-5,6-diethoxy-5,6-dimethyl-3-[[(E)-3-phenylprop-2-enoyl]oxymethyl]-1,4-dioxan-2-yl]methyl (E)-3-phenylprop-2-enoate
  参考文献：
  名称：

  Investigations of the Asymmetric Intramolecular [2 + 2] Photocycloaddition and Its Application as a Simple Access to Novel C₂-Symmetric Chelating Bisphosphanes Bearing a Cyclobutane Backbone

  摘要：

  The asymmetric intramolecular [2 + 2] photocycloaddition of alpha,beta-enoates was evaluated as a simple access to the novel Ct-symmetric bisphosphanes 22 and 27 possessing a cyclobutane backbone. A source of different chiral auxiliaries for investigations of the photochemical key step was provided by the transacetalization of dialkyl tartrates 3 with the corresponding 3,3-dialkoxybutan-2-ones 4. An insight into the selection mechanism was gained by temperature dependent measurements on the irradiation of the dicinnamates 10a-d, since the corresponding Eyring diagram discloses strictly linear functions as well as an isoselective relationship. Diol 8a turned out to be a structurally optimized auxiliary in terms of chiral induction and product crystallization and was also successfully applied in the first asymmetric photodimerization of 2-indenecarboxylic acid esters. Indeed, in this case excellent diastereoselectivities were achieved, too, but head-to-tail dimers 16a and 16b were formed predominantly. Diesters 11a and 16a were converted by standard procedures into the desired enantiopure 1,4-diphosphane 22 and 1,5-diphosphane 27. Furthermore, the hitherto unknown absolute configuration of delta-truxinic acid was elucidated from a single crystal X-ray structure analysis of 11a.

  DOI：

  10.1021/jo960556y

文献信息

• Investigations of the Asymmetric Intramolecular [2 + 2] Photocycloaddition and Its Application as a Simple Access to Novel <i>C</i>₂-Symmetric Chelating Bisphosphanes Bearing a Cyclobutane Backbone
  作者：Dieter Haag、Hans-Dieter Scharf

  DOI：10.1021/jo960556y

  日期：1996.1.1

  The asymmetric intramolecular [2 + 2] photocycloaddition of alpha,beta-enoates was evaluated as a simple access to the novel Ct-symmetric bisphosphanes 22 and 27 possessing a cyclobutane backbone. A source of different chiral auxiliaries for investigations of the photochemical key step was provided by the transacetalization of dialkyl tartrates 3 with the corresponding 3,3-dialkoxybutan-2-ones 4. An insight into the selection mechanism was gained by temperature dependent measurements on the irradiation of the dicinnamates 10a-d, since the corresponding Eyring diagram discloses strictly linear functions as well as an isoselective relationship. Diol 8a turned out to be a structurally optimized auxiliary in terms of chiral induction and product crystallization and was also successfully applied in the first asymmetric photodimerization of 2-indenecarboxylic acid esters. Indeed, in this case excellent diastereoselectivities were achieved, too, but head-to-tail dimers 16a and 16b were formed predominantly. Diesters 11a and 16a were converted by standard procedures into the desired enantiopure 1,4-diphosphane 22 and 1,5-diphosphane 27. Furthermore, the hitherto unknown absolute configuration of delta-truxinic acid was elucidated from a single crystal X-ray structure analysis of 11a.