(1R)-<1-(2)H>oct-2-ynyl formate | 144401-67-2

• 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: (1R)-<1-(2)H>oct-2-ynyl formate
• 英文别名: (1R)-(1-(2)H)oct-2-ynyl formate；[(1R)-1-deuteriooct-2-ynyl] formate
• CAS: 144401-67-2
• 化学式: C₉H₁₄O₂
• 分子量: 155.201
• InChiKey: BVIIYAAGZKVEOK-DLDGQBHASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  11
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R)-<1-(2)H>oct-2-ynyl formate 在 ammonium hydroxide 作用下， 以 甲醇 为溶剂， 以75%的产率得到(1R)-<1-(2)H>oct-2-yn-1-ol
  参考文献：
  名称：

  Synthesis of linoleic acid with chiral isotopic labelling at a flanking and a medial allylic methylene: the (8R,9Z,12Z)-[8-2H] and (11R,9Z,12Z)-[11-2H]-stereoisomers, and (Z)-[2,2-2H2]non-3-enal

  摘要：

  [1-H-2]Oct-2-ynal is converted by fermenting bakers' yeast into (1S)-[1-H-2]oct-2-yn-l-ol with an enantiomeric purity of > 96% as measured by Mosher's MTPA method. The alcohol, as its tosyl ester, was then converted by copper-catalysed coupling with the di-Grignard of dec-9-ynoic acid and catalytic semi-hydrogenation, into (11R)-[11-H-2]linoleic acid having less than 2% E-material and >95 atom %D. Provision for (11S)-[11-H-2]linoleic acid was made by configurational inversion of (1R) - [1-H-2]oct-2-yn-1-ol using Mitsunobu chemistry. (8R)-[8-H-2]Linoleic acid is made by a similar approach, the labelled chiral centre being formed on (8S)-8-hydroxy-[8-H-2]octanoic acid (> 96% ee). Reaction of the corresponding tosate with lithium acetylide-ethylenediamine complex gave, with configurational inversion, (8R)-[8-H-2]dec-9-ynoic acid, built into (8R)-[8-H-2]linoleic acid. A degradative circuit is applied to estimate the extent of configurational inversion in the displacement. Mitsunobu inversion of the (8S)-8-hydroxy compound provides access to (8S)-[8-H-2]linoleic acid. (Z)-Non-3-enal, a labile aldehyde from the enzymic degradation of linoleic acid, is made in [2,2-H-2(2)]-labelled form by a synthesis which uses, as a key step, the reaction between triheptynylborane and deuteriodiazoacetic ester.

  DOI：

  10.1039/p19920001929
• 作为产物：
  描述：

  <1,1-(2)H2>oct-2-yn-1-ol 在 manganese(IV) oxide 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 52.0h， 生成 (1R)-<1-(2)H>oct-2-ynyl formate
  参考文献：
  名称：

  Synthesis of linoleic acid with chiral isotopic labelling at a flanking and a medial allylic methylene: the (8R,9Z,12Z)-[8-2H] and (11R,9Z,12Z)-[11-2H]-stereoisomers, and (Z)-[2,2-2H2]non-3-enal

  摘要：

  [1-H-2]Oct-2-ynal is converted by fermenting bakers' yeast into (1S)-[1-H-2]oct-2-yn-l-ol with an enantiomeric purity of > 96% as measured by Mosher's MTPA method. The alcohol, as its tosyl ester, was then converted by copper-catalysed coupling with the di-Grignard of dec-9-ynoic acid and catalytic semi-hydrogenation, into (11R)-[11-H-2]linoleic acid having less than 2% E-material and >95 atom %D. Provision for (11S)-[11-H-2]linoleic acid was made by configurational inversion of (1R) - [1-H-2]oct-2-yn-1-ol using Mitsunobu chemistry. (8R)-[8-H-2]Linoleic acid is made by a similar approach, the labelled chiral centre being formed on (8S)-8-hydroxy-[8-H-2]octanoic acid (> 96% ee). Reaction of the corresponding tosate with lithium acetylide-ethylenediamine complex gave, with configurational inversion, (8R)-[8-H-2]dec-9-ynoic acid, built into (8R)-[8-H-2]linoleic acid. A degradative circuit is applied to estimate the extent of configurational inversion in the displacement. Mitsunobu inversion of the (8S)-8-hydroxy compound provides access to (8S)-[8-H-2]linoleic acid. (Z)-Non-3-enal, a labile aldehyde from the enzymic degradation of linoleic acid, is made in [2,2-H-2(2)]-labelled form by a synthesis which uses, as a key step, the reaction between triheptynylborane and deuteriodiazoacetic ester.

  DOI：

  10.1039/p19920001929