(S)-6-Oxabicyclo<3.1.0>hexane-1-methanol 3'-nitrobenzenesulfonate | 157999-12-7

• 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: (S)-6-Oxabicyclo<3.1.0>hexane-1-methanol 3'-nitrobenzenesulfonate
• 英文别名: (S)-6-Oxabicyclo[3.1.0]hexane-1-methanol 3'-nitrobenzenesulfonate；[(1S,5S)-6-oxabicyclo[3.1.0]hexan-1-yl]methyl 3-nitrobenzenesulfonate
• CAS: 157999-12-7
• 化学式: C₁₂H₁₃NO₆S
• 分子量: 299.304
• InChiKey: NKDSTASFRNENMN-RYUDHWBXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  110
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-6-Oxabicyclo<3.1.0>hexane-1-methanol 3'-nitrobenzenesulfonate 在 三氟甲磺酸 2,6-二叔丁基-4-甲基吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 132.0h， 生成 (1R,2S)-1,2-Bis(hexadecyloxy)-1-(hydroxymethyl)cyclopentane 3'-nitrobenzenesulfonate ester
  参考文献：
  名称：

  Synthesis of Chiral Diether and Tetraether Phospholipids: Regiospecific Ring Opening of Epoxy Alcohol Intermediates Derived from Asymmetric Epoxidation

  摘要：

  Diether and tetraether phospholipids have been synthesized using chiral epoxy alcohol starting materials (e.g. glycidol 3-nitrobenzenesulfonate esters or tert-butyldiphenylsilyl ethers). These chiral precursors provide control over the stereochemistry, substitution patterns, and steric properties of the phosphoglycerol backbone. Configuration at the sn-2 glycerol carbon was controlled by asymmetric epoxidation of allyl alcohol followed by acid-catalyzed, regioselective: Opening of the oxirane ring using excess aliphatic n-alcohols to give mono-O-alkylated glycerol intermediates in good yields. Nucleophilic attack at the less-hindered carbon of the oxirane ring was highly favored over attack at the sterically less accessible site, typically proceeding with regioselectivities of >10:1 and >95% ee's. Triflic acid, boron trifluoride etherate, toluenesulfonic acid, and tropylium tetrafluoroborate, all at 10 mol %, proved to be the most-effective catalysts compared with 10 % cesium fluoride, 10% magnesium chloride, or 20% DDQ based on (i) comparison of initial rates of product formation, (ii) regioselectivity of attack on the glycidol nucleus, and (iii) isolated yields of 3-O-alkyl-sn-glycerol 1-(3'-nitrobenzenesulfonates). Ether linked phospholipids, produced by alkylation of O-alkylglycerol sulfonates with excess n-alkyl triflates in the presence of equimolar 1,8-bis(dimethylamino)naphthalene, were isolated in 43-49 % overall yields (from glycidol 3-nitrobenzenesulfonate) after tetrabutylammonium hydroxide deprotection and phosphorylation; treatment of the 3-O-alkylglycerol sulfonates with tetrabutylammonium hydroxide prior to alkylation at the sn-2 center led to internal displacement and oxirane ring reformation, rather than hydrolysis to 3-O-alkylglycerol as described in J. Chromatogr. 1990, 506, 611. 3,3'-O-Polymethylene diglycerol phospholipids (bolaamphiphiles) were also prepared by this route using glycidol 3-nitrobenzenesulfonate and bifunctional alpha,omega-diols as nucleophiles. Synthesis of sterically demanding ether lipids, via Sharpless epoxidation of cyclopentene-1-methanol, produced materials that exhibited larger molecular areas than the analogous 1,2-di-O-alkylphosphatidic acids in monolayer experiments, confirming the restricted conformational flexibility of the cyclopentyl derivative at the air-water interface. Bolammphiphiles adopted a U-shaped conformation at the air-water interface. Elution-mode HPLC of racemic 3-O-hexadecyl-2-O-[(3',5'-dinitrophenyl) carbamoyl]glycerol 1-(3'-nitrobenzenesulfonate) on chiral naphthylalanine phases suggests that displacement-mode HPLC (Camacho-Torralba, P. L.; Vigh, G.; Thompson, D. H.; J. Chromatogr. 1993, 641, 31; 1993, 646, 259) may be used to obviate semipreparative chiral syntheses of alkyl glycerol ethers such as platelet activating factors, the antitumor agent ET-18-OCH3, and other biologically active ether lipids.

  DOI：

  10.1021/jo00090a011
• 作为产物：
  描述：

  环戊烯-1-基甲醇 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4-二甲氨基吡啶 、 (+)-Weinsaeure-diethylester 、 三乙胺 作用下， 反应 1.0h， 生成 (S)-6-Oxabicyclo<3.1.0>hexane-1-methanol 3'-nitrobenzenesulfonate
  参考文献：
  名称：

  Synthesis of Chiral Diether and Tetraether Phospholipids: Regiospecific Ring Opening of Epoxy Alcohol Intermediates Derived from Asymmetric Epoxidation

  摘要：

  Diether and tetraether phospholipids have been synthesized using chiral epoxy alcohol starting materials (e.g. glycidol 3-nitrobenzenesulfonate esters or tert-butyldiphenylsilyl ethers). These chiral precursors provide control over the stereochemistry, substitution patterns, and steric properties of the phosphoglycerol backbone. Configuration at the sn-2 glycerol carbon was controlled by asymmetric epoxidation of allyl alcohol followed by acid-catalyzed, regioselective: Opening of the oxirane ring using excess aliphatic n-alcohols to give mono-O-alkylated glycerol intermediates in good yields. Nucleophilic attack at the less-hindered carbon of the oxirane ring was highly favored over attack at the sterically less accessible site, typically proceeding with regioselectivities of >10:1 and >95% ee's. Triflic acid, boron trifluoride etherate, toluenesulfonic acid, and tropylium tetrafluoroborate, all at 10 mol %, proved to be the most-effective catalysts compared with 10 % cesium fluoride, 10% magnesium chloride, or 20% DDQ based on (i) comparison of initial rates of product formation, (ii) regioselectivity of attack on the glycidol nucleus, and (iii) isolated yields of 3-O-alkyl-sn-glycerol 1-(3'-nitrobenzenesulfonates). Ether linked phospholipids, produced by alkylation of O-alkylglycerol sulfonates with excess n-alkyl triflates in the presence of equimolar 1,8-bis(dimethylamino)naphthalene, were isolated in 43-49 % overall yields (from glycidol 3-nitrobenzenesulfonate) after tetrabutylammonium hydroxide deprotection and phosphorylation; treatment of the 3-O-alkylglycerol sulfonates with tetrabutylammonium hydroxide prior to alkylation at the sn-2 center led to internal displacement and oxirane ring reformation, rather than hydrolysis to 3-O-alkylglycerol as described in J. Chromatogr. 1990, 506, 611. 3,3'-O-Polymethylene diglycerol phospholipids (bolaamphiphiles) were also prepared by this route using glycidol 3-nitrobenzenesulfonate and bifunctional alpha,omega-diols as nucleophiles. Synthesis of sterically demanding ether lipids, via Sharpless epoxidation of cyclopentene-1-methanol, produced materials that exhibited larger molecular areas than the analogous 1,2-di-O-alkylphosphatidic acids in monolayer experiments, confirming the restricted conformational flexibility of the cyclopentyl derivative at the air-water interface. Bolammphiphiles adopted a U-shaped conformation at the air-water interface. Elution-mode HPLC of racemic 3-O-hexadecyl-2-O-[(3',5'-dinitrophenyl) carbamoyl]glycerol 1-(3'-nitrobenzenesulfonate) on chiral naphthylalanine phases suggests that displacement-mode HPLC (Camacho-Torralba, P. L.; Vigh, G.; Thompson, D. H.; J. Chromatogr. 1993, 641, 31; 1993, 646, 259) may be used to obviate semipreparative chiral syntheses of alkyl glycerol ethers such as platelet activating factors, the antitumor agent ET-18-OCH3, and other biologically active ether lipids.

  DOI：

  10.1021/jo00090a011

文献信息

• Synthesis of Chiral Diether and Tetraether Phospholipids: Regiospecific Ring Opening of Epoxy Alcohol Intermediates Derived from Asymmetric Epoxidation
  作者：David H. Thompson、Chris B. Svendsen、Ciro Di Meglio、Valerie C. Anderson

  DOI：10.1021/jo00090a011

  日期：1994.6

  Diether and tetraether phospholipids have been synthesized using chiral epoxy alcohol starting materials (e.g. glycidol 3-nitrobenzenesulfonate esters or tert-butyldiphenylsilyl ethers). These chiral precursors provide control over the stereochemistry, substitution patterns, and steric properties of the phosphoglycerol backbone. Configuration at the sn-2 glycerol carbon was controlled by asymmetric epoxidation of allyl alcohol followed by acid-catalyzed, regioselective: Opening of the oxirane ring using excess aliphatic n-alcohols to give mono-O-alkylated glycerol intermediates in good yields. Nucleophilic attack at the less-hindered carbon of the oxirane ring was highly favored over attack at the sterically less accessible site, typically proceeding with regioselectivities of >10:1 and >95% ee's. Triflic acid, boron trifluoride etherate, toluenesulfonic acid, and tropylium tetrafluoroborate, all at 10 mol %, proved to be the most-effective catalysts compared with 10 % cesium fluoride, 10% magnesium chloride, or 20% DDQ based on (i) comparison of initial rates of product formation, (ii) regioselectivity of attack on the glycidol nucleus, and (iii) isolated yields of 3-O-alkyl-sn-glycerol 1-(3'-nitrobenzenesulfonates). Ether linked phospholipids, produced by alkylation of O-alkylglycerol sulfonates with excess n-alkyl triflates in the presence of equimolar 1,8-bis(dimethylamino)naphthalene, were isolated in 43-49 % overall yields (from glycidol 3-nitrobenzenesulfonate) after tetrabutylammonium hydroxide deprotection and phosphorylation; treatment of the 3-O-alkylglycerol sulfonates with tetrabutylammonium hydroxide prior to alkylation at the sn-2 center led to internal displacement and oxirane ring reformation, rather than hydrolysis to 3-O-alkylglycerol as described in J. Chromatogr. 1990, 506, 611. 3,3'-O-Polymethylene diglycerol phospholipids (bolaamphiphiles) were also prepared by this route using glycidol 3-nitrobenzenesulfonate and bifunctional alpha,omega-diols as nucleophiles. Synthesis of sterically demanding ether lipids, via Sharpless epoxidation of cyclopentene-1-methanol, produced materials that exhibited larger molecular areas than the analogous 1,2-di-O-alkylphosphatidic acids in monolayer experiments, confirming the restricted conformational flexibility of the cyclopentyl derivative at the air-water interface. Bolammphiphiles adopted a U-shaped conformation at the air-water interface. Elution-mode HPLC of racemic 3-O-hexadecyl-2-O-[(3',5'-dinitrophenyl) carbamoyl]glycerol 1-(3'-nitrobenzenesulfonate) on chiral naphthylalanine phases suggests that displacement-mode HPLC (Camacho-Torralba, P. L.; Vigh, G.; Thompson, D. H.; J. Chromatogr. 1993, 641, 31; 1993, 646, 259) may be used to obviate semipreparative chiral syntheses of alkyl glycerol ethers such as platelet activating factors, the antitumor agent ET-18-OCH3, and other biologically active ether lipids.