(1R,2R,2'S,Z)-2-(9'-oxo-2',3',6',7',8',9'-hexahydrooxonin-2'-yl)cyclopropanecarbaldehyde | 164524-11-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1R,2R,2'S,Z)-2-(9'-oxo-2',3',6',7',8',9'-hexahydrooxonin-2'-yl)cyclopropanecarbaldehyde
• 英文别名: (1R,2R)-2-[(2S,4Z)-9-oxo-3,6,7,8-tetrahydro-2H-oxonin-2-yl]cyclopropane-1-carbaldehyde
• CAS: 164524-11-2
• 化学式: C₁₂H₁₆O₃
• 分子量: 208.257
• InChiKey: AZDPMNIIJVISAC-IGQKVBKWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1R,2R,2'S,Z)-2-(9'-oxo-2',3',6',7',8',9'-hexahydrooxonin-2'-yl)cyclopropanecarbaldehyde 在 chromium chloride 、 四丁基氟化铵 、 nickel dichloride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 6.0h， 生成 halicholactone
  参考文献：
  名称：

  Total Synthesis of Halicholactone and Neohalicholactone¹

  摘要：

  The total synthesis of the marine natural products neohalicholactone (1) and halicholactone (2), in enantiomerically pure form, are reported. Key steps in the synthesis of each compound include a cis-selective Wittig reaction, stereoselective cyclopropanation, nine-membered lactone formation using the Yamaguchi method and late-stage stereoselective Cr(II)/Ni(II) mediated coupling of vinyl iodides 39 and 50 with aldehyde 14. In the case of the neohalicholactone synthesis the two major components which were coupled in this convergent synthesis were each derived from the enantiomers of commercially available malic acid. The synthesis served to confirm the original assignment of absolute configuration which was made by Yamada and Clardy. We also demonstrated, through the preparation of diastereoisomers, that another reported compound closely related to neohalicholactone is likely to be the C-15 epimer 67.

  DOI：

  10.1021/jo962312j
• 作为产物：
  描述：

  (1R,2R)-2-((Z)-(S)-9-Oxo-2,3,6,7,8,9-hexahydro-oxonin-2-yl)-cyclopropanecarboxylic acid 在 sodium tetrahydroborate 、 N-甲基吲哚酮 、 四丙基高钌酸铵 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 三乙胺 为溶剂， 反应 0.83h， 生成 (1R,2R,2'S,Z)-2-(9'-oxo-2',3',6',7',8',9'-hexahydrooxonin-2'-yl)cyclopropanecarbaldehyde
  参考文献：
  名称：

  Total Synthesis of Halicholactone and Neohalicholactone¹

  摘要：

  The total synthesis of the marine natural products neohalicholactone (1) and halicholactone (2), in enantiomerically pure form, are reported. Key steps in the synthesis of each compound include a cis-selective Wittig reaction, stereoselective cyclopropanation, nine-membered lactone formation using the Yamaguchi method and late-stage stereoselective Cr(II)/Ni(II) mediated coupling of vinyl iodides 39 and 50 with aldehyde 14. In the case of the neohalicholactone synthesis the two major components which were coupled in this convergent synthesis were each derived from the enantiomers of commercially available malic acid. The synthesis served to confirm the original assignment of absolute configuration which was made by Yamada and Clardy. We also demonstrated, through the preparation of diastereoisomers, that another reported compound closely related to neohalicholactone is likely to be the C-15 epimer 67.

  DOI：

  10.1021/jo962312j

文献信息

• Total Synthesis of Halicholactone and Neohalicholactone
  作者：Jörg Pietruszka、Martina Bischop、Verena Doum、Anja Nordschild née Rieche、Diana Sandkuhl

  DOI：10.1055/s-0029-1217145

  日期：2010.2

  New total syntheses of the marine oxylipins halicholactone and neohalicholactone are presented. The key building blocks were synthesized utilizing chemoenzymatic methods. natural product - total synthesis - enzymes - boron reagents - asymmetric synthesis

  提出了新的海洋氧合素卤代内酯 和新卤代内酯的合成方法 。关键组成部分是利用化学酶法合成的。 天然产物-全合成-酶-硼试剂-不对称合成
• Application of Asymmetric Ylide Cyclopropanation in the Total Synthesis of Halicholactone
  作者：Chun-Yin Zhu、Xiao-Yu Cao、Ben-Hu Zhu、Chao Deng、Xiu-Li Sun、Bi-Qin Wang、Qi Shen、Yong Tang

  DOI：10.1002/chem.200901685

  日期：2009.11.2

  Efficient shortcut: The use of the well‐known cyclopropanation reaction provided facile access to the main fragment of halicholactone with excellent enantioselectivity and diastereoselectivity in only five steps (see scheme). This enabled the total synthesis of halicholactone with an overall yield of 11.2 % in the shortest synthetic route so far.

  高效的捷径：使用众所周知的环丙烷化反应，只需五个步骤即可轻松获得具有优异对映选择性和非对映选择性的卤代内酯的主要片段（参见方案）。这使得到目前为止，最短的合成路线能够以11.2％的总产率进行卤代内酯的全合成。
• The total asymmetric synthesis of Halicholactone and Neohalicholactone
  作者：Douglas J. Critcher、Stephen Connolly、Martin Wills

  DOI：10.1016/0040-4039(95)00588-4

  日期：1995.5

  Completion of the first total synthesis of the marine natural products Halicholactone and Neohalicholactone is reported. The key step is a moderately stereoselective coupling between a vinylic anion and an aldehyde. An unexpectedly slow desilylation due to the presence of a proximal hydroxy group is also reported.

  据报道已经完成了海洋天然产物卤代内酯和新卤代内酯的第一个全合成反应。关键步骤是乙烯基阴离子和醛之间的中等立体选择性偶联。还报道了由于近端羟基的存在而出乎意料的缓慢的甲硅烷基化。
• Stereoselective Synthesis of a Key Precursor of Halicholactone and Neohalicholactone
  作者：Debendra K. Mohapatra、Apurba Datta

  DOI：10.1021/jo971564x

  日期：1998.2.1

  An efficient synthesis of a known precursor of halicholactone (1a) and neohalicholactone (1b) has been developed using the strategically functionalized key cyclopropane intermediate 2, which in turn has been synthesized via stereoselective cyclopropanation of trans-cinnamyl alcohol in the presence of the chiral dioxaborolane ligand 4. Elaboration of the above bifunctional cyclopropane to the target molecule was achieved in a relatively short reaction sequence and in good overall yield, representing a formal synthesis of the title compounds.
• Total Synthesis of Halicholactone and Neohalicholactone¹
  作者：Douglas J. Critcher、Stephen Connolly、Martin Wills

  DOI：10.1021/jo962312j

  日期：1997.9.1

  The total synthesis of the marine natural products neohalicholactone (1) and halicholactone (2), in enantiomerically pure form, are reported. Key steps in the synthesis of each compound include a cis-selective Wittig reaction, stereoselective cyclopropanation, nine-membered lactone formation using the Yamaguchi method and late-stage stereoselective Cr(II)/Ni(II) mediated coupling of vinyl iodides 39 and 50 with aldehyde 14. In the case of the neohalicholactone synthesis the two major components which were coupled in this convergent synthesis were each derived from the enantiomers of commercially available malic acid. The synthesis served to confirm the original assignment of absolute configuration which was made by Yamada and Clardy. We also demonstrated, through the preparation of diastereoisomers, that another reported compound closely related to neohalicholactone is likely to be the C-15 epimer 67.