2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl acetate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl acetate
• 化学式: C₂₃H₃₅F₃N₂O₂Sn
• 分子量: 547.248
• InChiKey: UTQJMYWCIHPORU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.99
• 重原子数：
  31.0
• 可旋转键数：
  13.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  51.02
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl acetate 在 氨 作用下， 以 甲醇 、 乙醚 为溶剂， 以97%的产率得到2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol
  参考文献：
  名称：

  2-(Tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl Alcohol: A Building Block for Photolabeling and Crosslinking Reagents of Very High Specific Radioactivity

  摘要：

  A general approach for the synthesis of novel, radioiodinated photolabeling and cross-linking reagents at no-carrier-added (nea) specific radioactivity (> 2000 Ci/mmol) is described. In this approach, 2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol 12 serves as a module which, through acylation of its alcohol function, is connected to other structural/functional elements to make the tin-containing precursor forms of the reagents. The final, radioactive compounds are then conveniently prepared in yields varying from 15-50% by electrophilic aromatic substitution of the tributylstannyl group by I-125(+) generated in situ from I-125(-) by peracetic acid. Using this approach, we have synthesized two analogues of phosphatidylcholine (PC) (20 and 21), an analogue of ceramide (36), as well as two heterobifunctional label-transfer cross-linkers (29 and 33). PC 21, examined more closely, is a substrate of the PC-specific phospholipid exchange protein from beef liver and of phospholipase D from cabbage. The latter was utilized to enzymatically convert PC 21 into two additional phospholipids, phosphatidylserine (PS) 25 and phosphatidic acid (PA) 26. Reagents that contain this iodinated photophor also combine desirable photochemical properties. Thus, evidence is presented that they undergo efficient photolysis to generate a (singlet) carbene intermediate which inserts efficiently into hydrocarbon CH bonds. In addition, we demonstrate that the diazirine can be photolyzed in a selective manner, that is, without photodeiodination to occur to a significant extent.

  DOI：

  10.1021/ja00116a013
• 作为产物：
  描述：

  六正丁基二锡 、 2-iodo-4-<3-(trifluoromethyl)-3H-diazirin-3-yl>benzyl acetate 在 KH₂PO₄nBu₄NF 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 以36%的产率得到2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl acetate
  参考文献：
  名称：

  2-(Tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl Alcohol: A Building Block for Photolabeling and Crosslinking Reagents of Very High Specific Radioactivity

  摘要：

  A general approach for the synthesis of novel, radioiodinated photolabeling and cross-linking reagents at no-carrier-added (nea) specific radioactivity (> 2000 Ci/mmol) is described. In this approach, 2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol 12 serves as a module which, through acylation of its alcohol function, is connected to other structural/functional elements to make the tin-containing precursor forms of the reagents. The final, radioactive compounds are then conveniently prepared in yields varying from 15-50% by electrophilic aromatic substitution of the tributylstannyl group by I-125(+) generated in situ from I-125(-) by peracetic acid. Using this approach, we have synthesized two analogues of phosphatidylcholine (PC) (20 and 21), an analogue of ceramide (36), as well as two heterobifunctional label-transfer cross-linkers (29 and 33). PC 21, examined more closely, is a substrate of the PC-specific phospholipid exchange protein from beef liver and of phospholipase D from cabbage. The latter was utilized to enzymatically convert PC 21 into two additional phospholipids, phosphatidylserine (PS) 25 and phosphatidic acid (PA) 26. Reagents that contain this iodinated photophor also combine desirable photochemical properties. Thus, evidence is presented that they undergo efficient photolysis to generate a (singlet) carbene intermediate which inserts efficiently into hydrocarbon CH bonds. In addition, we demonstrate that the diazirine can be photolyzed in a selective manner, that is, without photodeiodination to occur to a significant extent.

  DOI：

  10.1021/ja00116a013

文献信息

• 2-(Tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl Alcohol: A Building Block for Photolabeling and Crosslinking Reagents of Very High Specific Radioactivity
  作者：Thomas Weber、Josef Brunner

  DOI：10.1021/ja00116a013

  日期：1995.3

  A general approach for the synthesis of novel, radioiodinated photolabeling and cross-linking reagents at no-carrier-added (nea) specific radioactivity (> 2000 Ci/mmol) is described. In this approach, 2-(tributylstannyl)-4-[3-(trifluoromethyl)-3H-diazirin-3-yl]benzyl alcohol 12 serves as a module which, through acylation of its alcohol function, is connected to other structural/functional elements to make the tin-containing precursor forms of the reagents. The final, radioactive compounds are then conveniently prepared in yields varying from 15-50% by electrophilic aromatic substitution of the tributylstannyl group by I-125(+) generated in situ from I-125(-) by peracetic acid. Using this approach, we have synthesized two analogues of phosphatidylcholine (PC) (20 and 21), an analogue of ceramide (36), as well as two heterobifunctional label-transfer cross-linkers (29 and 33). PC 21, examined more closely, is a substrate of the PC-specific phospholipid exchange protein from beef liver and of phospholipase D from cabbage. The latter was utilized to enzymatically convert PC 21 into two additional phospholipids, phosphatidylserine (PS) 25 and phosphatidic acid (PA) 26. Reagents that contain this iodinated photophor also combine desirable photochemical properties. Thus, evidence is presented that they undergo efficient photolysis to generate a (singlet) carbene intermediate which inserts efficiently into hydrocarbon CH bonds. In addition, we demonstrate that the diazirine can be photolyzed in a selective manner, that is, without photodeiodination to occur to a significant extent.