(-)-dehydrovomifoliol | 39763-38-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (-)-dehydrovomifoliol
• 英文别名: (-)-(R)-dehydrovomifoliol；(6R)-dehydrovomifoliol；(4R)-4-hydroxy-3,5,5-trimethyl-4-[(E)-3-oxobut-1-enyl]cyclohex-2-en-1-one
• CAS: 39763-38-7
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: JJRYPZMXNLLZFH-GFUIURDCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (-)-dehydrovomifoliol 在 palladium/alumina 氢气 、 三乙胺 、 三氯氧磷 作用下， 生成 (R)-8,9-dehydrotheaspirone
  参考文献：
  名称：

  2-Hydroxy-2,6,10,10-tetramethyl-1-oxaspiro[4.5]dec-6-en-8-one:  Precursor of 8,9-Dehydrotheaspirone in White-Fleshed Nectarines

  摘要：

  2-Hydroxy-2,6,10,10-tetramethyl-1-oxaspiro[4.5]dec-6-en-8-one (2) was identified as precursor of 2,6,10,10-tetramethyl-1-oxaspiro[4.5]deca-2,6-dien-8-one (8,9-dehydrotheaspirone, 1) in an Et2O extract from white-fleshed nectarine (Prunus persica Batsch var. nucipersica Schneid) juice. The identification was verified by comparison of chromatographic and spectral data (MS, H-1 and C-13 NMR) of the new natural product with those of an authentic reference compound synthesized from dehydrovomifoliol (3). NMR spectral data revealed that the precursor compound 2 is present in 5:1 mixture of diastereomeric hemiacetals 2a/b. The absolute stereochemistry of the diastereoisomers (major isomer, 2S,5S; minor isomer, 2R,5S) was elucidated by NOE experiments and dehydration to optically pure (S-configured) spiroether 1. In addition to hemiacetals 2a/b, (6S)-dehydrovomifoliol (3) as well as the beta-D-glucoside of (3S,5R,6S)-3-hydroxy-5,6-epoxy-beta-ionone (5) was also identified in nectarine juice.

  DOI：

  10.1021/jf960598n
• 作为产物：
  描述：

  (3S,5S,6R)-3-acetoxy-5,6-epoxy-5,6-dihydro-β-ionon 生成 (-)-dehydrovomifoliol
  参考文献：
  名称：

  旋光草grass酮和脱氢伏米福尔的合成，作为（+）-脱落酸绝对构型的合成支持物

  摘要：

  以天然和光学活性形式合成了酮（5）和脱氢伏米福尔（6）。评论了这项工作与（+）-脱落酸（3）的（S）-立体化学有关的重要性。的多种位阻CO基团的不寻常的选择性氢化7，得到9被记录。

  DOI：

  10.1016/s0040-4020(01)97270-9

文献信息

• The asymmetric total synthesis of (−)-dehydrovomifoliol. The penultimate precursor to (−)-abscisic acid (ABA)
  作者：A.I. Meyers、Michael A. Sturgess

  DOI：10.1016/s0040-4039(00)99568-6

  日期：——

  A formal total synthesis of (−)-ABA from the chiral bicyclic lactam (3) has been accomplished in nine steps.

  从手性双环内酰胺（3）正式合成（-）-ABA的过程共分9个步骤。
• Chemoenzymatic resolution of cis- and trans-3,6-dihydroxy-α-ionone. Synthesis of the enantiomeric forms of dehydrovomifoliol and 8,9-dehydrotheaspirone
  作者：Stefano Serra、Assem Barakat、Claudio Fuganti

  DOI：10.1016/j.tetasy.2007.10.014

  日期：2007.10

  A straightforward synthesis of both enantiomers of cis- and trans-3-acetoxy-6-hydroxy-alpha-ionone is described. The title compounds are prepared by resolution of the diastereoisomerically pure racemic 3,6-dihydroxy-alpha-ionone isomers. The latter process is based on two steps. The first is the enantio- and regioselective lipase-mediated acetylation of diols to afford the corresponding 3-acetoxy-derivatives. The second is the fractional crystallization of the latter compounds that increase their enantiomeric purity. These building blocks were used for the synthesis of both enantiomeric forms of the natural norterpenoids dehydrovomifoliol 3 and 8,9-dehydrotheaspirone 5. The latter compound is a natural flavor and its odor properties were evaluated by professional perfumers. (c) 2007 Elsevier Ltd. All rights reserved.
• MEYERS, A. I.;STURGESS, MICHAEL A., TETRAHEDRON LETT., 30,(1989) N4, C. 1741-1744
  作者：MEYERS, A. I.、STURGESS, MICHAEL A.

  DOI：——

  日期：——
• Syntheses of optically active grasshopper ketone and dehydrovomifoliol as a synthetic support for the revised absolute configuration of (+)-abscisic acid
  作者：K. Mori

  DOI：10.1016/s0040-4020(01)97270-9

  日期：1974.1

  Grasshopper ketone (5) and dehydrovomifoliol (6) were synthesized in their natural and optically active forms. Comments were made on the significance of this work in relation to the (S)-stereochemistry of (+)-abscisic acid (3). Unusual selective hydrogenation of the more hindered CO group of 7 to give 9 is recorded.

  以天然和光学活性形式合成了酮（5）和脱氢伏米福尔（6）。评论了这项工作与（+）-脱落酸（3）的（S）-立体化学有关的重要性。的多种位阻CO基团的不寻常的选择性氢化7，得到9被记录。
• 2-Hydroxy-2,6,10,10-tetramethyl-1-oxaspiro[4.5]dec-6-en-8-one:  Precursor of 8,9-Dehydrotheaspirone in White-Fleshed Nectarines
  作者：Holger Knapp、Cornelia Weigand、Jürgen Gloser、Peter Winterhalter

  DOI：10.1021/jf960598n

  日期：1997.4.1

  2-Hydroxy-2,6,10,10-tetramethyl-1-oxaspiro[4.5]dec-6-en-8-one (2) was identified as precursor of 2,6,10,10-tetramethyl-1-oxaspiro[4.5]deca-2,6-dien-8-one (8,9-dehydrotheaspirone, 1) in an Et2O extract from white-fleshed nectarine (Prunus persica Batsch var. nucipersica Schneid) juice. The identification was verified by comparison of chromatographic and spectral data (MS, H-1 and C-13 NMR) of the new natural product with those of an authentic reference compound synthesized from dehydrovomifoliol (3). NMR spectral data revealed that the precursor compound 2 is present in 5:1 mixture of diastereomeric hemiacetals 2a/b. The absolute stereochemistry of the diastereoisomers (major isomer, 2S,5S; minor isomer, 2R,5S) was elucidated by NOE experiments and dehydration to optically pure (S-configured) spiroether 1. In addition to hemiacetals 2a/b, (6S)-dehydrovomifoliol (3) as well as the beta-D-glucoside of (3S,5R,6S)-3-hydroxy-5,6-epoxy-beta-ionone (5) was also identified in nectarine juice.