(1R,5R)-6-oxabicyclo[3.1.0]hexan-1-ylmethanol | 360578-68-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧烷类
• 英文名称: (1R,5R)-6-oxabicyclo[3.1.0]hexan-1-ylmethanol
• 英文别名: (R)-6-Oxabicyclo[3.1.0]hexane-1-methanol；[(1R,5R)-6-oxabicyclo[3.1.0]hexan-1-yl]methanol
• CAS: 360578-68-3
• 化学式: C₆H₁₀O₂
• 分子量: 114.144
• InChiKey: JRKHPRUFBGRXQH-PHDIDXHHSA-N

物化性质

• 沸点：
  206.2±8.0 °C(Predicted)
• 密度：
  1.242±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0
• 重原子数：
  8
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R,5R)-6-oxabicyclo[3.1.0]hexan-1-ylmethanol 在 三氟甲磺酸 4-二甲氨基吡啶 、 2,6-二叔丁基-4-甲基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 168.0h， 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 、 (-)-diethyl tartrate 作用下， 反应 1.0h， 生成 (1R,5R)-6-oxabicyclo[3.1.0]hexan-1-ylmethanol
  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

• Fluorinated Organocatalysts for the Enantioselective Epoxidation of Enals: Molecular Preorganisation by the Fluorine-Iminium Ion Gauche Effect
  作者：Eva-Maria Tanzer、Lucie E. Zimmer、W. Bernd Schweizer、Ryan Gilmour

  DOI：10.1002/chem.201201316

  日期：2012.9.3

  The fluorine‐iminium ion gauche effect is triggered upon union of a secondary β‐fluoroamine and an α,β‐unsaturated aldehyde, providing a useful strategy for controlling the molecular topology of intermediates that are central to organocatalytic processes. The β‐fluoroamine (S)‐2‐(fluorodiphenylmethyl)pyrrolidine (1) is an effective catalyst for the enantioselective epoxidation of α,β‐unsaturated aldehydes

  当仲β-氟胺和α，β-不饱和醛结合后会触发氟亚胺离子的网状效应，为控制有机催化过程中重要的中间体的分子拓扑提供了有用的策略。β-氟胺（S）-2-（氟二苯基甲基）吡咯烷（1）是α，β-不饱和醛对映选择性环氧化的有效催化剂。结构编辑的过程表明，该催化剂的效率归因于嵌入在β-氟亚胺基序中的（氟二苯基）甲基。1催化具有挑战性的环状α，β-二取代，β，β-二取代和α，β，β-三取代的烯醛继续进行优异的对映体控制（高达98％  ee）。
• Catalytic asymmetric epoxidation
  申请人：Yamamoto Hisashi

  公开号：US20050159607A1

  公开（公告）日：2005-07-21

  The present invention relates to the synthesis of chiral epoxides via a catalytic asymmetric oxidation of olefins. Additionally, the methodology provides a method of asymmetrically oxidizing sulfides and phosphines. This asymmetric oxidation employs a catalyst system composed of a metal and a chiral bishydroxamic acid ligand, which, in the presence of a stoichiometric oxidation reagent, serves to asymmetrically oxidize a variety of substrates.

  本发明涉及通过催化不对称氧化烯烃合成手性环氧化物。此外，该方法提供了一种不对称氧化硫醚和膦的方法。这种不对称氧化利用了由金属和手性双羟羧酸配体组成的催化剂体系，该体系在存在化学计量氧化试剂的情况下，用于不对称氧化各种底物。
• Design of Optically Active Hydroxamic Acids as Ligands in Vanadium-Catalyzed Asymmetric Epoxidation
  作者：Yujiro Hoshino、Noriaki Murase、Masataka Oishi、Hisashi Yamamoto

  DOI：10.1246/bcsj.73.1653

  日期：2000.7

  New optically active hydroxamic acids bearing a 1,1′-binaphthyl group were prepared as ligands in a vanadium-catalyzed asymmetric epoxidation. The feature of these hydroxamic acids is a sterically hindered ligand. The asymmetric epoxidation with good selectivity and reactivity can be established by using VO(O-i-Pr)3 (5 mol%) and a small excess amount of ligand (7.5 mol%) with triphenylmethyl hydroperoxide

  在钒催化的不对称环氧化反应中，制备了带有 1,1'-联萘基团的新型旋光异羟肟酸作为配体。这些异羟肟酸的特征是空间位阻配体。在-20 °C 的甲苯中，使用 VO(Oi-Pr)3 (5 mol%) 和少量过量的配体 (7.5 mol%) 与三苯甲基氢过氧化物 (TrOOH) 可以建立具有良好选择性和反应性的不对称环氧化反应. 二取代的烯丙醇比单取代或三取代的烯丙醇环氧化得更快，并且以良好到高的对映选择性 (48-94%ee) 获得。讨论了基于 1e 的 X 射线晶体结构的过渡态。
• Chiral Vanadium-Based Catalysts for Asymmetric Epoxidation of Allylic Alcohols
  作者：Noriaki Murase、Yujiro Hoshino、Masataka Oishi、Hisashi Yamamoto

  DOI：10.1021/jo9821933

  日期：1999.1.1
• 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.