1-[tert-butyl(diphenyl)silyl]oxy-3-[(Z)-hexadec-1-enoxy]propan-2-ol | 187266-73-5

• 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-[tert-butyl(diphenyl)silyl]oxy-3-[(Z)-hexadec-1-enoxy]propan-2-ol
• CAS: 187266-73-5
• 化学式: C₃₅H₅₆O₃Si
• 分子量: 552.913
• InChiKey: DYGZBYMRHADCJX-OLFWJLLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.55
• 重原子数：
  39
• 可旋转键数：
  22
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  1-[tert-butyl(diphenyl)silyl]oxy-3-[(Z)-hexadec-1-enoxy]propan-2-ol 在 吡啶 、 三(二甲氨基)锍二氟三甲基硅酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.17h， 生成 3-hexadecanoyl-1-O-(1'-hexadecenyl)-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
• 作为产物：
  描述：

  甘油烯丙基醚 在 咪唑 、 仲丁基锂 作用下， 以 四氢呋喃 、 环己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.17h， 生成 1-[tert-butyl(diphenyl)silyl]oxy-3-[(Z)-hexadec-1-enoxy]propan-2-ol
  参考文献：
  名称：

  Direct Synthesis of Plasmenylcholine from Allyl-Substituted Glycerols

  摘要：

  We report a new method for the facile preparation of plasmenylcholine via reaction of lithioalkoxy allyl intermediates with 1-iodoalkanes as the key step in the stereoselective formation of 1'-(Z)-alkenyl glyceryl ethers. The allyl anion intermediate is prepared by treating mono- or disiloxyprotected 1-allylglycerol precursors with s-BuLi at -65 to -80degreesC. Subsequent addition of 1-iodoalkane solutions at low temperature gives moderate yields of gamma-coupled, Z-vinyl ethers as the major product and alpha-coupled product as the minor component. Several different preparative strategies for the total synthesis of plasmalogens are enabled by this simple transformation.

  DOI：

  10.1021/jo026826w

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.
• Direct Synthesis of Plasmenylcholine from Allyl-Substituted Glycerols
  作者：Junhwa Shin、David H. Thompson

  DOI：10.1021/jo026826w

  日期：2003.8.1

  We report a new method for the facile preparation of plasmenylcholine via reaction of lithioalkoxy allyl intermediates with 1-iodoalkanes as the key step in the stereoselective formation of 1'-(Z)-alkenyl glyceryl ethers. The allyl anion intermediate is prepared by treating mono- or disiloxyprotected 1-allylglycerol precursors with s-BuLi at -65 to -80degreesC. Subsequent addition of 1-iodoalkane solutions at low temperature gives moderate yields of gamma-coupled, Z-vinyl ethers as the major product and alpha-coupled product as the minor component. Several different preparative strategies for the total synthesis of plasmalogens are enabled by this simple transformation.