1,2-di-O-((Z)-1'-hexadecenyl)-3-(tert-butyldiphenylsilyl)-rac-glycerol | 163586-67-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 甘油脂
• 英文名称: 1,2-di-O-((Z)-1'-hexadecenyl)-3-(tert-butyldiphenylsilyl)-rac-glycerol
• 英文别名: 2,3-bis[(Z)-hexadec-1-enoxy]propoxy-tert-butyl-diphenylsilane
• CAS: 163586-67-2
• 化学式: C₅₁H₈₆O₃Si
• 分子量: 775.328
• InChiKey: YUEGQAKGFGBPCV-HRNZYLNSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  15.17
• 重原子数：
  55
• 可旋转键数：
  37
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1,2-di-O-((Z)-1'-hexadecenyl)-3-(tert-butyldiphenylsilyl)-rac-glycerol 在 sodium hydroxide 、 三乙胺 作用下， 以 乙醇 、 苯 为溶剂， 反应 28.5h， 生成
  参考文献：
  名称：

  Stereocontrolled Synthesis of Plasmalogen-Type Lipids from Glyceryl Ester Precursors

  摘要：

  Two pathways for the synthesis of naturally occurring Z vinyl ether linkages in plasmalogen lipids (1-O-((Z)-1'-alkenyl)-2-acyl-sn-glycerophosphocholines and ethanolamines) have been investigated: (i) reduction of alpha-alkoxy enol phosphates and (ii) alkylidenation of diprotected glyceryl 1-formate esters utilizing 1,1-dibromoalkanes, zinc, TiCl4, and TMEDA. While both methods reported good chemical yields and high Z selectivity for model substrates, the titanium-mediated coupling sequence failed when the dibromoalkyl chain length exceeded Ca, Treatment of 1-decyl-2-O-benzyl-3-O-(tert-butyldiphenylsilyl) with LDA and diethyl chlorophosphate at -78 degrees C followed by reduction of the vinyl phosphate intermediate using Pd(PPh(3))4 and Et(3)Al in DCE at 0 degrees C, however, gave 1-O-(1'-decenyl)2-O-benzyl-3-O-(tert-butyldiphenylsilyl)-rac-glycerol in in 62-65% yield and 2:1 Z:E stereoselectivity; reduction in hexane at 0 OC with slow addition of :triethylaluminum improved the selectivity to > 95% Z. Extension of this method to the preparation of a plasmalogen precursor (1-O-((Z)-1'-hexadecenyl)-2-hexadecanoyl and the first synthesis of a choline derivative of diplasmalogen (1,2-di(O-(Z)-1'-hexadecenyl)-rac-glycerophosphocholine), a major component of rabbit epididymal spermatozoa phospholipid, in moderate chemical yields and excellent Z selectivity is reported.

  DOI：

  10.1021/jo00098a040
• 作为产物：
  描述：

  1,2-二棕榈酰-rac-丙三醇 在 咪唑 、 四(三苯基膦)钯 、 三乙基铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 27.83h， 生成 1,2-di-O-((Z)-1'-hexadecenyl)-3-(tert-butyldiphenylsilyl)-rac-glycerol
  参考文献：
  名称：

  Stereocontrolled Synthesis of Plasmalogen-Type Lipids from Glyceryl Ester Precursors

  摘要：

  Two pathways for the synthesis of naturally occurring Z vinyl ether linkages in plasmalogen lipids (1-O-((Z)-1'-alkenyl)-2-acyl-sn-glycerophosphocholines and ethanolamines) have been investigated: (i) reduction of alpha-alkoxy enol phosphates and (ii) alkylidenation of diprotected glyceryl 1-formate esters utilizing 1,1-dibromoalkanes, zinc, TiCl4, and TMEDA. While both methods reported good chemical yields and high Z selectivity for model substrates, the titanium-mediated coupling sequence failed when the dibromoalkyl chain length exceeded Ca, Treatment of 1-decyl-2-O-benzyl-3-O-(tert-butyldiphenylsilyl) with LDA and diethyl chlorophosphate at -78 degrees C followed by reduction of the vinyl phosphate intermediate using Pd(PPh(3))4 and Et(3)Al in DCE at 0 degrees C, however, gave 1-O-(1'-decenyl)2-O-benzyl-3-O-(tert-butyldiphenylsilyl)-rac-glycerol in in 62-65% yield and 2:1 Z:E stereoselectivity; reduction in hexane at 0 OC with slow addition of :triethylaluminum improved the selectivity to > 95% Z. Extension of this method to the preparation of a plasmalogen precursor (1-O-((Z)-1'-hexadecenyl)-2-hexadecanoyl and the first synthesis of a choline derivative of diplasmalogen (1,2-di(O-(Z)-1'-hexadecenyl)-rac-glycerophosphocholine), a major component of rabbit epididymal spermatozoa phospholipid, in moderate chemical yields and excellent Z selectivity is reported.

  DOI：

  10.1021/jo00098a040

文献信息

• Stereocontrolled Synthesis of Plasmalogen-Type Lipids from Glyceryl Ester Precursors
  作者：Yuanjin Rui、David H. Thompson

  DOI：10.1021/jo00098a040

  日期：1994.9

  Two pathways for the synthesis of naturally occurring Z vinyl ether linkages in plasmalogen lipids (1-O-((Z)-1'-alkenyl)-2-acyl-sn-glycerophosphocholines and ethanolamines) have been investigated: (i) reduction of alpha-alkoxy enol phosphates and (ii) alkylidenation of diprotected glyceryl 1-formate esters utilizing 1,1-dibromoalkanes, zinc, TiCl4, and TMEDA. While both methods reported good chemical yields and high Z selectivity for model substrates, the titanium-mediated coupling sequence failed when the dibromoalkyl chain length exceeded Ca, Treatment of 1-decyl-2-O-benzyl-3-O-(tert-butyldiphenylsilyl) with LDA and diethyl chlorophosphate at -78 degrees C followed by reduction of the vinyl phosphate intermediate using Pd(PPh(3))4 and Et(3)Al in DCE at 0 degrees C, however, gave 1-O-(1'-decenyl)2-O-benzyl-3-O-(tert-butyldiphenylsilyl)-rac-glycerol in in 62-65% yield and 2:1 Z:E stereoselectivity; reduction in hexane at 0 OC with slow addition of :triethylaluminum improved the selectivity to > 95% Z. Extension of this method to the preparation of a plasmalogen precursor (1-O-((Z)-1'-hexadecenyl)-2-hexadecanoyl and the first synthesis of a choline derivative of diplasmalogen (1,2-di(O-(Z)-1'-hexadecenyl)-rac-glycerophosphocholine), a major component of rabbit epididymal spermatozoa phospholipid, in moderate chemical yields and excellent Z selectivity is reported.