2,3:5,6-O-diisopropylidene-4-O-(tert-butyldimethylsilyl)-D-myo-inositol | 151637-22-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3:5,6-O-diisopropylidene-4-O-(tert-butyldimethylsilyl)-D-myo-inositol
• CAS: 151637-22-8
• 化学式: C₁₈H₃₄O₆Si
• 分子量: 374.55
• InChiKey: HUHBHQIYOLPESS-SOAFEQHCSA-N

物化性质

• 沸点：
  422.7±45.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.79
• 重原子数：
  25.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.38
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  2,3:5,6-O-diisopropylidene-4-O-(tert-butyldimethylsilyl)-D-myo-inositol 在 叔丁基过氧化氢 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 4.75h， 生成 O-(1,2-O-di-n-hexanoyl-sn-3-glyceryl) O-(D-2',3':5',6'-O-diisopropylidene-4'-O-(tert-butyldimethylsilyl)-myo-inositol) O-(2''-(trimethylsilyl)ethyl) phosphate
  参考文献：
  名称：

  General Method for the Synthesis of Phospholipid Derivatives of 1,2-O-Diacyl-sn-Glycerols

  摘要：

  An efficient phosphite coupling protocol is described for the syntheses of the major classes of phospholipids that are derived from 1,2-O-diacyl-sn-glycerols and analogues thereof. The symmetrical diacyl glycerols 10c,d were prepared by straightforward acylation of 3-O-benzyl-sn-glycerol (7) with the appropriate carboxylic acid in the presence of dicyclohexylcarbodiimide (DCC) and 4-(dimethylamino)pyridine (DMAP). A simple method for preparing saturated and unstaturated mixed 1,2-O-diacyl-sn-glycerols was then devised that involved stepwise acylation of 7 with different alkyl carboxylic acids and debenzylation this procedure is exemplified by the preparation of 10a,b. The 1,2-O-diacyl-sn-glycerols 10a-d were then coupled with suitably protected lipid head groups employing reactive alkyl or aryl dichlorophosphites to give intermediate phosphite triesters in high overall yields. Oxidation or sulfurization of these phosphites proceeded smoothly to give the corresponding phosphate or phosphorothioate triesters, deprotection of which then provided the phosphatidylcholines 16 and 17, the phosphatidylethanolamine 20, the phosphatidylserine 28, and the phosphatidylinositols 37 and 38. Preparation of 37 and 38 required the invention of an improved method for resolving the isopropylidene-protected D-myo-inositol derivative 33. This phosphite coupling procedure was modified to assemble phospholipids bearing-polyunsaturated acyl side chains at the sn-2-position as exemplified by the preparation of the phosphatidylethanolamine 26. The one-pot phosphite coupling procedure is also applicable to the syntheses of a variety of other biologically interesting phospholipid analogues. For example, the phosphatidylinositol analogues 49-51, in which the hydroxyl group at C(2) of the inositol ring has been modified, were prepared in excellent overall yields by conjoining the 1,2-O-diacyl-sn-glycerol 10c with the protected inositol derivatives 44, 45, and 48. Phospholipid analogues that contain other replacements of the phosphate group including phosphoramidates and thiophosphates maybe prepared as evidenced by the syntheses of 56 and 61 in which the sn-3 oxygen atom of the 1,2-O-diacyl-sn-glycerol moiety is replaced with an N-benzyl group or a sulfur atom, respectively.

  DOI：

  10.1021/jo00096a023
• 作为产物：
  描述：

  1-O-camphanoyl-2,3:5,6-O-diisopropylidene-4-O-(tert-butyldimethylsilyl)-D-myo-inositol 在 氢氧化钾 作用下， 以 甲醇 为溶剂， 反应 0.33h， 以94%的产率得到2,3:5,6-O-diisopropylidene-4-O-(tert-butyldimethylsilyl)-D-myo-inositol
  参考文献：
  名称：

  General Method for the Synthesis of Phospholipid Derivatives of 1,2-O-Diacyl-sn-Glycerols

  摘要：

  An efficient phosphite coupling protocol is described for the syntheses of the major classes of phospholipids that are derived from 1,2-O-diacyl-sn-glycerols and analogues thereof. The symmetrical diacyl glycerols 10c,d were prepared by straightforward acylation of 3-O-benzyl-sn-glycerol (7) with the appropriate carboxylic acid in the presence of dicyclohexylcarbodiimide (DCC) and 4-(dimethylamino)pyridine (DMAP). A simple method for preparing saturated and unstaturated mixed 1,2-O-diacyl-sn-glycerols was then devised that involved stepwise acylation of 7 with different alkyl carboxylic acids and debenzylation this procedure is exemplified by the preparation of 10a,b. The 1,2-O-diacyl-sn-glycerols 10a-d were then coupled with suitably protected lipid head groups employing reactive alkyl or aryl dichlorophosphites to give intermediate phosphite triesters in high overall yields. Oxidation or sulfurization of these phosphites proceeded smoothly to give the corresponding phosphate or phosphorothioate triesters, deprotection of which then provided the phosphatidylcholines 16 and 17, the phosphatidylethanolamine 20, the phosphatidylserine 28, and the phosphatidylinositols 37 and 38. Preparation of 37 and 38 required the invention of an improved method for resolving the isopropylidene-protected D-myo-inositol derivative 33. This phosphite coupling procedure was modified to assemble phospholipids bearing-polyunsaturated acyl side chains at the sn-2-position as exemplified by the preparation of the phosphatidylethanolamine 26. The one-pot phosphite coupling procedure is also applicable to the syntheses of a variety of other biologically interesting phospholipid analogues. For example, the phosphatidylinositol analogues 49-51, in which the hydroxyl group at C(2) of the inositol ring has been modified, were prepared in excellent overall yields by conjoining the 1,2-O-diacyl-sn-glycerol 10c with the protected inositol derivatives 44, 45, and 48. Phospholipid analogues that contain other replacements of the phosphate group including phosphoramidates and thiophosphates maybe prepared as evidenced by the syntheses of 56 and 61 in which the sn-3 oxygen atom of the 1,2-O-diacyl-sn-glycerol moiety is replaced with an N-benzyl group or a sulfur atom, respectively.

  DOI：

  10.1021/jo00096a023

文献信息

• Synthesis and Kinetic Evaluation of Inhibitors of the Phosphatidylinositol-Specific Phospholipase C from <i>Bacillus cereus</i>
  作者：Stephen F. Martin、Allan S. Wagman

  DOI：10.1021/jo960850q

  日期：1996.11.15

  Substrate analogues of phosphatidylinositol (1) were synthesized and evaluated as potential inhibitors of the bacterial phosphatidylinositol-specific phospholipase C (PI-PLC) from Bacillus cereus. The chiral analogues of the water-soluble phospholipid substrate 5 were designed to probe the effects of varying the inositol C-2 hydroxyl group, which is generally believed to serve as the nucleophile in

  合成了磷脂酰肌醇（1）的底物类似物，并评估为蜡状芽孢杆菌的细菌磷脂酰肌醇特异性磷脂酶C（PI-PLC）的潜在抑制剂。水溶性磷脂底物5的手性类似物被设计成探测改变肌醇C-2羟基的作用，通常认为它通过PI-PLC在磷脂酰肌醇水解的第一步中用作亲核试剂。在类似物6-9中，磷脂酰肌醇衍生物的肌醇环上的C-2羟基以几种方式被合理地改变。肌醇环C-2处的立体化学颠倒导致了scyllo衍生物6。肌醇C-2羟基被氟取代，以产生烷基-氟代肌醇7，氢原子被取代以提供2-脱氧化合物8。C-2羟基被O-甲基化以制备甲氧基衍生物9. C-2处的天然肌醇构型保留在不可水解的二硫代磷酸酯类似物10中。然后使用D-肌醇1-（4-硝基苯基）在连续测定法中分析这些类似物对PI-PLC的抑制作用（25）作为发色底物。确定了每种磷脂酰肌醇衍生物的动力学参数，发现它们是具有K（i）的竞争性抑制剂，如下：6,0.2mM; 10，0.6毫米;
• General Route to Phosphonodithioic Acid Derivatives
  作者：Stephen F. Martin、Allan S. Wagman、G. Greg Zipp、Mikhail K. Gratchev

  DOI：10.1021/jo00105a007

  日期：1994.12

  A general procedure for the synthesis of esters of phosphonodithioic acids has been developed. The method involves the reaction of the Grignard reagents 2a-h with 2-chloro-1,3,2-dithiaphospholane (1) to give 3a-h that were sulfurized using elemental sulfur to furnish the intermediate phosphonotrithioates 4a-h, reaction of which with a variety of alcohols in the presence of DBU furnished the desired phosphonodithioates 5a-h and 6-9.
• A general and efficient route to phosphorodithioate analogs of naturally occurring lipids
  作者：Stephen F. Martin、Allan S. Wagman

  DOI：10.1021/jo00074a012

  日期：1993.10

  A general procedure has been developed for the efficient synthesis of lipid phosphorodithioate analogues 14a-f from 2-alkoxy-2-thio-1,3,2-dithiaphospholanes 13a-c, which are readily prepared from 2-chloro-1,3,2-dithiaphospholane (11) by sequential reaction with an alcohol and elemental sulfur.