(1S,2S,3R,4R)-1,2-diphenyl-3,4-bis([(tolyl-4-sulfonyl)oxy]methyl)cyclobutane | 181785-24-0

• 分子结构分类: 有机化合物 - 木脂素、新木脂素和相关化合物 - 环丁烷木脂素
• 英文名称: (1S,2S,3R,4R)-1,2-diphenyl-3,4-bis([(tolyl-4-sulfonyl)oxy]methyl)cyclobutane
• 英文别名: [(1R,2R,3S,4S)-2-[(4-methylphenyl)sulfonyloxymethyl]-3,4-diphenylcyclobutyl]methyl 4-methylbenzenesulfonate
• CAS: 181785-24-0
• 化学式: C₃₂H₃₂O₆S₂
• 分子量: 576.734
• InChiKey: NEYOPKCSKVNFFL-GASGPIRDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  40
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  104
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  lithium boranyl-diphenyl-phosphanide 、 (1S,2S,3R,4R)-1,2-diphenyl-3,4-bis([(tolyl-4-sulfonyl)oxy]methyl)cyclobutane 在 tetrafluoroboric acid dimethyl ether complex 作用下， 生成 (1R,2R,3S,4S)-1,2-bis((diphenylphosphanyl)methyl)-3,4-diphenylcyclobutane
  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：

  [(2S,3S,5R,6R)-5,6-dimethoxy-5,6-dimethyl-3-[[(E)-3-phenylprop-2-enoyl]oxymethyl]-1,4-dioxan-2-yl]methyl (E)-3-phenylprop-2-enoate 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 、 甲苯 为溶剂， 反应 75.0h， 生成 (1S,2S,3R,4R)-1,2-diphenyl-3,4-bis([(tolyl-4-sulfonyl)oxy]methyl)cyclobutane
  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

• Aggregate Formation and Photoreactivity in Phospholipid Vesicles and Langmuir-Blodgett Multilayers: Topologically Controlled Photodimerization of Amphiphilic Styrenes
  作者：Xiao-Mei Zhao、Jerome Perlstein、David G. Whitten

  DOI：10.1021/ja00102a012

  日期：1994.11

  The amphiphilic styrene fatty acid 1 and its corresponding phosphatidylcholine derivative 2 have been found to exhibit aggregate formation and topologically controlled photodimerization in Langmuir-Blodgett (LB) assemblies and phospholipid vesicles, respectively. For both compounds, formation of the beta or syn, head-to-head photodimer is the chief photoreaction observed upon irradiation in the assemblies; a trace of the cis styrene is observed on irradiation in the phospholipid vesicles. Changes in the absorption spectrum and a lack of fluorescence in the assemblies, compared to dilute organic solutions, suggest that 1 and 2 exist as ''H'' aggregates in both the LB films and vesicles. Monte Carlo simulations suggest that the most stable structure in a monolayer is a simple translation aggregate. Energy minimization gives a cross sectional area in good agreement with that measured for films at the air-water interface. The calculated structure has nearest neighbor separation within the ''magic distance'' for solid state photodimerization of 4.10 Angstrom. The relatively small calculated tilt angle suggests that dimers can be formed without substantial reorganization. The lambda(max) for the aggregate estimated by an extended dipole calculation shows good agreement with the measured absorption maximum. Vesicles of 2, either pure or with excess saturated phospholipid, give topologically controlled formation of the beta dimer via photolysis of an aggregated form.
• 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.