(3R,4R)-3,4-dihydroxy-4-methylhex-5-ynenitrile | 1266113-82-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,4R)-3,4-dihydroxy-4-methylhex-5-ynenitrile
• CAS: 1266113-82-9
• 化学式: C₇H₉NO₂
• 分子量: 139.154
• InChiKey: UCNNOFUPALOTGZ-RNFRBKRXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  64.2
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (3R,4R)-3,4-dihydroxy-4-methylhex-5-ynenitrile 在 盐酸 作用下， 以 乙醚 为溶剂， 反应 48.0h， 以90%的产率得到(4R,5R)-5-ethynyl-4,5-dihydro-4-hydroxy-5-methyl-3H-furan-2-ylideneamine hydrochloride
  参考文献：
  名称：

  A Serendipitous Synthesis of (+)-Gregatin B, Second Structure Revisions of the Aspertetronins, Gregatins, and Graminin A, Structure Revision of the Penicilliols

  摘要：

  A (DHQN)(2)AQN-promoted asymmetric dihydroxylation (92% ee) of the allyl chloride derived from enynol (E)-13 and an 8-step sequence provided access to the hydroxyethylated furanone (R)-21. Oxidation with MnO(2) furnished 50% furanone (+)-(R)-2a and 2.7% isomeric furanone (+)-(R)-3a. (R)-2a possesses the accepted constitution of (+)-gregatin B but its spectra are different. Surprisingly, (+)-(R)-3a equals the natural product. Analogous structure reassignments are due for the gregatins A and C-E, the aspertetronins A-B, graminin A, and the penicilliols A and B.

  DOI：

  10.1021/ol2008318
• 作为产物：
  描述：

  1-Chlor-3-methyl-pent-2-en-4-in 在 potassium osmate(VI) dihydrate 、 18-冠醚-6 、 甲基磺酰胺 、 碳酸氢钠 、 potassium carbonate 、 氢化奎宁 1,4-(2,3-二氮杂萘)二醚 、 potassium hexacyanoferrate(III) 作用下， 以 水 、 乙腈 、 叔丁醇 为溶剂， 反应 72.0h， 生成 (3R,4R)-3,4-dihydroxy-4-methylhex-5-ynenitrile
  参考文献：
  名称：

  带有三取代的C═C键的烯炔的不对称二羟基化反应。具有四级立体中心的前所未有的通往γ-内酯构建基的途径

  摘要：

  途中将获得一组全面的羟基内酯结构单元（4 R，5 R）-，（4 R，5 S）-，（4 S，5 R）-和（4 S，5 S）-5a，Sharpless不对称进行了烯丙基氯化物（E）-和（Z）-9的二羟基化。他们提供了具有高达92％ee和绝对构型的四种二醇10立体异构体，事实证明它们符合Sharpless助记符。

  DOI：

  10.1021/ol103061g

文献信息

• Asymmetric Dihydroxylations of Enynes with a Trisubstituted C═C Bond. An Unprecedented Route to γ-Lactone Building Blocks with a Quaternary Stereocenter
  作者：Heike Burghart-Stoll、Tobias Kapferer、Reinhard Brückner

  DOI：10.1021/ol103061g

  日期：2011.3.4

  comprehensive set of hydroxylactone building blocks (4R,5R)-, (4R,5S)-, (4S,5R)-, and (4S,5S)-5a, Sharpless asymmetric dihydroxylations of allylic chlorides (E)- and (Z)-9 were performed. They delivered the four stereoisomers of diol 10 with up to 92% ee and absolute configurations, which were proven to be in accordance with the Sharpless mnemonic.

  途中将获得一组全面的羟基内酯结构单元（4 R，5 R）-，（4 R，5 S）-，（4 S，5 R）-和（4 S，5 S）-5a，Sharpless不对称进行了烯丙基氯化物（E）-和（Z）-9的二羟基化。他们提供了具有高达92％ee和绝对构型的四种二醇10立体异构体，事实证明它们符合Sharpless助记符。
• A Serendipitous Synthesis of (+)-Gregatin B, Second Structure Revisions of the Aspertetronins, Gregatins, and Graminin A, Structure Revision of the Penicilliols
  作者：Heike Burghart-Stoll、Reinhard Brückner

  DOI：10.1021/ol2008318

  日期：2011.5.20

  A (DHQN)(2)AQN-promoted asymmetric dihydroxylation (92% ee) of the allyl chloride derived from enynol (E)-13 and an 8-step sequence provided access to the hydroxyethylated furanone (R)-21. Oxidation with MnO(2) furnished 50% furanone (+)-(R)-2a and 2.7% isomeric furanone (+)-(R)-3a. (R)-2a possesses the accepted constitution of (+)-gregatin B but its spectra are different. Surprisingly, (+)-(R)-3a equals the natural product. Analogous structure reassignments are due for the gregatins A and C-E, the aspertetronins A-B, graminin A, and the penicilliols A and B.