(2R,3R,4E)-1,2-O-cyclohexylidene-4-octadecene-1,2,3-triol | 471907-66-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2R,3R,4E)-1,2-O-cyclohexylidene-4-octadecene-1,2,3-triol
• 英文别名: (E,1R)-1-[(3R)-1,4-dioxaspiro[4.5]decan-3-yl]hexadec-2-en-1-ol
• CAS: 471907-66-1
• 化学式: C₂₄H₄₄O₃
• 分子量: 380.612
• InChiKey: NQUPAWCXVWHORI-DNXBDCAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.1
• 重原子数：
  27
• 可旋转键数：
  14
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R,4E)-1,2-O-cyclohexylidene-4-octadecene-1,2,3-triol 在 吡啶 、 sodium azide 、 三氟乙酸 作用下， 以 吡啶 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 9.0h， 生成 [(E,2S,3R)-2-azido-1-[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxyoctadec-4-en-3-yl] benzoate
  参考文献：
  名称：

  Chemoenzymatic stereoconvergent synthesis of 3-O-benzoyl azidosphingosine

  摘要：

  The synthesis of 3-O-benzoyl azidosphingosine 1 through a stereoconvergent approach is described. Nucleophilic addition of the Grignard reagent of 1-pentadecyne to cyclohexylidene-D-glyceraldehyde results in a mixture of diastereoisomeric propargylic alcohols. Subsequent enzymatic separation of these diastereoisomers, mediated by lipase from Candida antarctica, Mitsunobu inversion on the wrong diastereoisomer and extremely efficient introduction of azide using a chloromesylate leaving group affords the title compound in 30% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00201-x
• 作为产物：
  描述：

  (2R,3R)-1,2-O-cyclohexylidene-4-octadecyne-1,2,3-triol 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 5.0h， 以0.78 g的产率得到(2R,3R,4E)-1,2-O-cyclohexylidene-4-octadecene-1,2,3-triol
  参考文献：
  名称：

  Chemoenzymatic stereoconvergent synthesis of 3-O-benzoyl azidosphingosine

  摘要：

  The synthesis of 3-O-benzoyl azidosphingosine 1 through a stereoconvergent approach is described. Nucleophilic addition of the Grignard reagent of 1-pentadecyne to cyclohexylidene-D-glyceraldehyde results in a mixture of diastereoisomeric propargylic alcohols. Subsequent enzymatic separation of these diastereoisomers, mediated by lipase from Candida antarctica, Mitsunobu inversion on the wrong diastereoisomer and extremely efficient introduction of azide using a chloromesylate leaving group affords the title compound in 30% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00201-x

文献信息

• Lewis Acid-Catalyzed Addition of Alkenylzirconocenes to Carbonyl Compounds: Remarkable Activity of Trimethylsilyl Triflate
  作者：Teiichi Murakami、Kiyotaka Furusawa

  DOI：10.1055/s-2004-829108

  日期：——

  Addition of 1-pentadecenylzirconocene chloride to 2,3-O-cyclohexylidene-(R)-glyceraldehyde in CH 2 Cl 2 was best promoted by trimethylsilyl triflate (TMSOTf) to give the diastereomeric anti- and syn-alcohols in 80% yield. TMSOTf also showed remarkable catalytic activity for the addition of 1(E)-alkenylzirconocenes to ketones, giving tertiary allylic alcohols in good yields.

  三甲基甲硅烷基三氟甲磺酸酯 (TMSOTf) 可以最好地促进将 1-十五碳烯基二茂锆氯化物添加到 CH 2 Cl 2 中的 2,3-O-亚环己基-(R)-甘油醛中，从而以 80% 的收率得到非对映异构体反醇和顺醇。TMSOTf 还显示出显着的催化活性，可将 1(E)-alkenylzirconocenes 添加到酮中，从而以良好的收率生成烯丙基叔醇。