(+)-(6R)-(2E)-8-tert-butyldimethylsilyloxy-2,6-dimethyloct-2-en-1-ol | 141208-73-3

• 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: (+)-(6R)-(2E)-8-tert-butyldimethylsilyloxy-2,6-dimethyloct-2-en-1-ol
• 英文别名: (2E,6R)-8-{[Tert-butyl(dimethyl)silyl]oxy}-2,6-dimethyl-2-octen-1-OL；(E,6R)-8-[tert-butyl(dimethyl)silyl]oxy-2,6-dimethyloct-2-en-1-ol
• CAS: 141208-73-3
• 化学式: C₁₆H₃₄O₂Si
• 分子量: 286.53
• InChiKey: KHJYKPMIZISDCZ-MFYHJKBNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.75
• 重原子数：
  19
• 可旋转键数：
  9
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (+)-(6R)-(2E)-8-tert-butyldimethylsilyloxy-2,6-dimethyloct-2-en-1-ol 在 镍 吡啶 、 lithium hydroxide 、 silver(I) nitrite 、 硼酸三甲酯 、 四丁基氟化铵 、 氢气 、 对氯苯异氰酸酯 、 三乙胺 、 N,N-二异丙基乙胺 、 sodium iodide 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 丙酮 、 苯 为溶剂， 25.0 ℃ 、196.12 kPa 条件下， 反应 108.0h， 生成 (+)-薄荷呋喃
  参考文献：
  名称：

  Furanoterpene Synthesis via Intramolecular Nitrile Oxide Cycloaddition Reaction: A Total Synthesis of (+)-Menthofuran

  摘要：

  A fused furan assembling strategy based on an intramolecular [3+2] dipolar cycloaddition reaction of nitrile oxide has been applied to a total synthesis of perfumy furanomonoterpene (+)-menthofuran (1). The key cycloaddition substrates (9) and (1 2) are easily prepared via straightforward routes starting from (+)-citronellal and these are treated with sodium hypochlorite and p-chlorophenyl isocyanate, respectively. The cycloaddition reactions generate 10 : 1 mixture of diastereoisomeric isoxazolines (2a) and (2b) in good to excellent yields. The isoxazolines (2a,b) thus obtained are converted to (+)-menthofuran (1) by sequential reductive hydrolysis and alkaline hydrolysis (or vice versa) followed by acid treatment of the resulting beta,gamma-dihydroxy ketone (1 4).

  DOI：

  10.3987/com-92-6231
• 作为产物：
  描述：

  (+)-香茅醛 在 咪唑 、 叔丁基过氧化氢 、 sodium tetrahydroborate 、 selenium(IV) oxide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 (+)-(6R)-(2E)-8-tert-butyldimethylsilyloxy-2,6-dimethyloct-2-en-1-ol
  参考文献：
  名称：

  Furanoterpene Synthesis via Intramolecular Nitrile Oxide Cycloaddition Reaction: A Total Synthesis of (+)-Menthofuran

  摘要：

  A fused furan assembling strategy based on an intramolecular [3+2] dipolar cycloaddition reaction of nitrile oxide has been applied to a total synthesis of perfumy furanomonoterpene (+)-menthofuran (1). The key cycloaddition substrates (9) and (1 2) are easily prepared via straightforward routes starting from (+)-citronellal and these are treated with sodium hypochlorite and p-chlorophenyl isocyanate, respectively. The cycloaddition reactions generate 10 : 1 mixture of diastereoisomeric isoxazolines (2a) and (2b) in good to excellent yields. The isoxazolines (2a,b) thus obtained are converted to (+)-menthofuran (1) by sequential reductive hydrolysis and alkaline hydrolysis (or vice versa) followed by acid treatment of the resulting beta,gamma-dihydroxy ketone (1 4).

  DOI：

  10.3987/com-92-6231

文献信息

• Straightforward Synthesis of Chiral Terpenoid Building Blocks by Ru-Catalyzed Enantioselective Hydrogenation
  作者：Johal Ruiz、Philippe Oger、Laurent Soulère、Florence Popowycz

  DOI：10.1021/acs.joc.1c00677

  日期：2021.7.16

  Starting from commercially available (R)- and (S)-β-citronellol, two strategies were designed to synthesize all four stereoisomers of 2,6-dimethyloctane monoterpene chirons in four or five steps in 32–47% overall yield. The desired fragments were obtained by a key Ru-catalyzed asymmetric olefin hydrogenation step under moderate temperature (50 °C), pressure (4 bar), and low catalyst loadings (0.5 mol

  从市售的 ( R )- 和 ( S )-β-香茅醇开始，设计了两种策略，以 32-47% 的总产率分四步或五步合成 2,6-二甲基辛烷单萜 chirons 的所有四种立体异构体。在中等温度 (50 °C)、压力 (4 bar) 和低催化剂负载 (0.5 mol%) 下，在优化条件下，通过关键的 Ru 催化的不对称烯烃氢化步骤获得所需的片段。筛选市售催化剂突出了 DM-SEGPHOS 作为经济上有利的替代品，可替代常用的 H8-BINAP 以获得相同的性能。这些结果为这些有用构建块的多功能和可扩展合成开辟了新的可能性。
• Total Synthesis of (+)-Menthofuran
  作者：Kozo Shishido、Takeshi Takata、Koji Umimoto、Masayuki Shibuya

  DOI：10.3987/com-91-s19

  日期：——

  Total synthesis of optically active menthofuran, a perfumy monoterpene, has been accomplished employing the intramolecular [3 + 2] cycloaddition-based methodology for the construction of fused furans.
• Furanoterpene Synthesis via Intramolecular Nitrile Oxide Cycloaddition Reaction: A Total Synthesis of (+)-Menthofuran
  作者：Kozo Shishido、Koji Umimoto、Takeshi Takata、Osamu Irie、Masayuki Shibuya

  DOI：10.3987/com-92-6231

  日期：——

  A fused furan assembling strategy based on an intramolecular [3+2] dipolar cycloaddition reaction of nitrile oxide has been applied to a total synthesis of perfumy furanomonoterpene (+)-menthofuran (1). The key cycloaddition substrates (9) and (1 2) are easily prepared via straightforward routes starting from (+)-citronellal and these are treated with sodium hypochlorite and p-chlorophenyl isocyanate, respectively. The cycloaddition reactions generate 10 : 1 mixture of diastereoisomeric isoxazolines (2a) and (2b) in good to excellent yields. The isoxazolines (2a,b) thus obtained are converted to (+)-menthofuran (1) by sequential reductive hydrolysis and alkaline hydrolysis (or vice versa) followed by acid treatment of the resulting beta,gamma-dihydroxy ketone (1 4).