(E)-(4R,5S)-4-Hydroxy-5-methyl-oct-6-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-(4R,5S)-4-Hydroxy-5-methyl-oct-6-en-2-one
• 英文别名: (E,4R,5S)-4-hydroxy-5-methyloct-6-en-2-one
• 化学式: C₉H₁₆O₂
• 分子量: 156.225
• InChiKey: YGPKNMVTUONJFE-HXOXMVQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-(4R,5S)-4-Hydroxy-5-methyl-oct-6-en-2-one 在 sodium tetrahydroborate 、 二甲基硫 、 三乙基硼 、 臭氧 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 (2R,3R,4R,6R)-3,6-Dimethyl-tetrahydro-pyran-2,4-diol
  参考文献：
  名称：

  Tandem Oxyallylations and Retro-ene Eliminations. One Pot Stereoselective Synthesis of Polypropionate Fragments with Three Contiguous Stereogenic Centers and One (E)-Alkene Unit.

  摘要：

  Mixtures of (EE)-2-methyl-1-silyloxypenta-1,3-dienes, enoxysilanes, SO2 and (t-Bu)Me2SiOTf (catalyst) generate (Z)-5-alkyl-1,3-dimethyl-6-oxo-4-silyloxyalk-2-enesulfinic acids that undergo stereoselective retro-ene eliminations of SO2 with the formation of corresponding (E)-3-hydroxy-2-alkyl-4-methylalk-5-en-1-ones with 2,3-syn and 3,4-anti diastereoselectivity. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01398-1
• 作为产物：
  描述：

  (E,E)-2-methyl-1-[(tert-butyldimethylsilyl)oxy]-1,3-pentadiene 在 叔丁基二甲硅基三氟甲磺酸酯 、 氢氟酸 、 二氧化硫 、 水 、 氯化铵 作用下， 以 乙腈 为溶剂， 反应 20.0h， 生成 (E)-(4R,5S)-4-Hydroxy-5-methyl-oct-6-en-2-one
  参考文献：
  名称：

  Tandem Oxyallylations and Retro-ene Eliminations. One Pot Stereoselective Synthesis of Polypropionate Fragments with Three Contiguous Stereogenic Centers and One (E)-Alkene Unit.

  摘要：

  Mixtures of (EE)-2-methyl-1-silyloxypenta-1,3-dienes, enoxysilanes, SO2 and (t-Bu)Me2SiOTf (catalyst) generate (Z)-5-alkyl-1,3-dimethyl-6-oxo-4-silyloxyalk-2-enesulfinic acids that undergo stereoselective retro-ene eliminations of SO2 with the formation of corresponding (E)-3-hydroxy-2-alkyl-4-methylalk-5-en-1-ones with 2,3-syn and 3,4-anti diastereoselectivity. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0040-4039(97)01398-1

文献信息

• Palladium-Catalyzed Conversion of β,γ-Unsaturated Silyl Sulfinates into (<i>E</i>)-Alkenes:  Asymmetric Synthesis of Polypropionate Fragments
  作者：Xiaogen Huang、Cotinica Craita、Pierre Vogel

  DOI：10.1021/jo0357622

  日期：2004.6.1

  At low temperature, 1-alkoxy-1,3-dienes add to sulfur dioxide activated by a Lewis or protic acid generating zwitterionic intermediates that can be quenched by enoxysilanes. The resulting β,γ-unsaturated silyl sulfinates can be desilylated by 1:1 Pd(OAc)2/PPh3 catalyst, liberating the corresponding β,γ-unsaturated sulfinic acids that undergo smooth and highly stereoselective retro-ene eliminations

  在低温下，将1-烷氧基-1,3-二烯添加到路易斯或质子酸活化的二氧化硫中，生成两性离子中间体，该中间体可被环氧硅烷淬灭。可以用1：1 Pd（OAc）2 / PPh 3催化剂将所得的β，γ-不饱和甲硅烷基亚磺酸盐脱甲硅基，从而释放出相应的β，γ-不饱和亚磺酸，后者经过顺滑和高度立体选择性的逆向二氧化硫消除。该方法已应用于产生对映体纯的聚丙烯酸酯片段。
• Silyl methallylsulfinates: efficient and powerful agents for the chemoselective silylation of alcohols, polyols, phenols and carboxylic acids
  作者：Xiaogen Huang、Cotinica Craita、Loay Awad、Pierre Vogel

  DOI：10.1039/b417894g

  日期：——

  Alcohols, phenols and carboxylic acids are silylated with very good yields in the presence of silyl methallylsulfinates under non-basic conditions and with the formation of volatile co-products.

  在无碱条件下，在硅烷美克基亚基亚基亚基亚基亚基硫酸盐的存在下，醇、酚和羧酸以很高的产率进行硅化，同时生成挥发性副产品。
• Tandem Oxyallylations and Retro-ene Eliminations. One Pot Stereoselective Synthesis of Polypropionate Fragments with Three Contiguous Stereogenic Centers and One (E)-Alkene Unit.
  作者：Jean-Michel Roulet、Geneviève Puhr、Pierre Vogel

  DOI：10.1016/s0040-4039(97)01398-1

  日期：1997.9

  Mixtures of (EE)-2-methyl-1-silyloxypenta-1,3-dienes, enoxysilanes, SO2 and (t-Bu)Me2SiOTf (catalyst) generate (Z)-5-alkyl-1,3-dimethyl-6-oxo-4-silyloxyalk-2-enesulfinic acids that undergo stereoselective retro-ene eliminations of SO2 with the formation of corresponding (E)-3-hydroxy-2-alkyl-4-methylalk-5-en-1-ones with 2,3-syn and 3,4-anti diastereoselectivity. (C) 1997 Elsevier Science Ltd.