(2R,3R,5r,6s)-5,6-diethoxy-5,6-dimethyl[1,4]dioxane-2,3-dicarboxylic acid diethyl ester

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,3R,5r,6s)-5,6-diethoxy-5,6-dimethyl[1,4]dioxane-2,3-dicarboxylic acid diethyl ester
• 英文别名: diethyl (2R,3R,5S,6R)-5,6-diethoxy-5,6-dimethyl-1,4-dioxane-2,3-dicarboxylate
• 化学式: C₁₆H₂₈O₈
• 分子量: 348.394
• InChiKey: VODQVTBJRXEBRJ-BHTHQVBYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  89.5
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为产物：
  描述：

  L-(+)-酒石酸二乙酯 、 3,3-二乙氧基-2-丁酮 在 对甲苯磺酸 作用下， 60.0 ℃ 、5.33 kPa 条件下， 生成 (2R,3R,5R,6R)-5,6-diethoxy-5,6-dimethyl<1,4>dioxane-2,3-dicarboxylic acid diethyl ester 、 (2R,3R,5S,6S)-5,6-diethoxy-5,6-dimethyl[1,4]dioxane-2,3-dicarboxylic acid diethyl ester 、 (2R,3R,5r,6s)-5,6-diethoxy-5,6-dimethyl[1,4]dioxane-2,3-dicarboxylic acid diethyl ester
  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.