(3S,4R)-4-cyclohexyl-3-methyl-1-buten-4-ol | 121155-51-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4R)-4-cyclohexyl-3-methyl-1-buten-4-ol
• 英文别名: (1R,2S)-1-cyclohexyl-2-methylbut-3-en-1-ol
• CAS: 121155-51-9
• 化学式: C₁₁H₂₀O
• 分子量: 168.279
• InChiKey: DTRSBSFLBIIIIC-ONGXEEELSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S,4R)-4-cyclohexyl-3-methyl-1-buten-4-ol 在 Rh/Al₂O₃ 氢气 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 生成 (1S,2S)-1-cyclohexyl-2-methylbutan-1-ol
  参考文献：
  名称：

  使用酒石酸二异丙酯修饰的 (E)-和 (Z)-巴豆基硼酸酯进行不对称合成：手性巴豆基硼酸酯的制备和与非手性醛的反应

  摘要：

  巴豆基硼酸酯与脂肪族（线性或 α-单支链；72-91% ee）、芳香族和 α,β-不饱和醛（55-74% ee）发生高度非对映选择性和对映选择性反应。反应的非对映选择性与试剂异构体纯度密切相关，特别是对于在 -78 o C 下进行的反应。对所有底物的对映选择性在甲苯中最佳，但苯甲醛除外，因为苯甲醛在 THF 中获得最佳结果。本研究中合成的 14 种高烯丙醇中有 9 种的相对和绝对立体化学是通过与 Sharpless 不对称环氧化制备的环氧醇的相关性来确定的

  DOI：

  10.1021/ja00173a023
• 作为产物：
  描述：

  (E,1R,2S)-1-cyclohexyl-2-methyl-4-tributylstannylbut-3-en-1-ol 在 正丁基锂 、 氯化铵 作用下， 生成 (3S,4R)-4-cyclohexyl-3-methyl-1-buten-4-ol
  参考文献：
  名称：

  Enantioconvergent Hydroboration of a Racemic Allene: Enantioselective Synthesis of (E)-δ-Stannyl-anti-homoallylic Alcohols via Aldehyde Crotylboration

  摘要：

  The enantioconvergent hydroboration of racemic allenylstannane (+/-)-1 with ((d)Ipc)(2)BH converts both enantiomers of (+/-)-1 into the enantioenriched crotylborane (S)-E-3. Subsequent crotylboration of aldehydes with (S)-E-3 provides (E)-stannyl-homoallylic alcohols 5 in good yields and with excellent enantioselectivity.

  DOI：

  10.1021/ja2010187

文献信息

• Enantioselective synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: Reactions with achiral aldehydes
  作者：William R. Roush、Kaori Ando、Daniel B. Powers、Ronald L. Halterman、Alan D. Palkowitz

  DOI：10.1016/s0040-4039(00)80816-3

  日期：1988.1

  The reactions of diisopropyl tartrate modified( E)- and (Z)-crotylboronates with representative achiral aldehydes are described. Enantioselectivity ranges from 55–91% e.e. depending on the aldehyde employed.

  描述了酒石酸二异丙酯改性的（E）-和（Z）-巴豆基硼酸酯与代表性的非手性醛的反应。对映选择性范围为55–91％ee，具体取决于所用的醛。
• SYNTHESIS OF (S,S)-DIISOPROPYL TARTRATE (E)-CROTYLBORONATE AND ITS REACTION WITH ALDEHYDES: (2R,3R,4R)-1,2-DIDEOXY-2-ETHENYL-4,5-O-(1-METHYLETHYLIDENE)-XYLITOL
  作者：Sun, Huikai、Roush, William R.

  DOI：10.15227/orgsyn.088.0181

  日期：——
• N,N'-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide: An Improved Chiral Auxiliary for the Asymmetric Allylboration Reaction
  作者：William R. Roush、Paul T. Grover

  DOI：10.1021/jo00117a036

  日期：1995.6

  N,N-Bis(2,2,2-trifluoroethyl)-N,N'-ethylenetartramide (8), synthesized by a simple four-step sequence from ethylenediamine and benzylidenetartaric acid, was designed in anticipation that the derived allylboronates 9-11 would display enhanced reactivity owing to the inductive effect of the N-trifluoroethyl substituents that would increase the Lewis acidity of the boron atom of the B-allyl-1,3,2-dioxaborolanes. Reagents 9-11 were synthesized by transesterification of 8 with the crystalline and easily purified allylboronate diethanolamine complexes 13, 19, and 25. Allylboronate 9 is ca. 100-fold more reactive than 6 and is also substantially more useful than the previously reported allyboronate 4, which suffers from very poor solubility in toluene at -78 degrees C. Most importantly, allylboronates 9-11 are significantly more enantioselective than the parent tartrate allylboronates 1-3 and rank among the most highly enantioselective allylboron reagents yet reported. Reactions of 9-11 with aldehydes are performed in THF at- -78 or -55 degrees C for 5-12 h periods. The enantioselectivity realized in reactions with achiral aldehydes is 92-95% ee (Table 2), and excellent diastereoselectivity is achieved in double asymmetric reactions with chiral aldehydes 15a, 15b, and 33 (Tables 3 and 4). For example, 16 and 28 are now available with a minimum selectivity of 92% from reactions of 15a and 15b with allylboronate 9, while the crotylboration products 29, 30, and 31 are available with a minimum selectivity of 90% (usually greater than or equal to 95%) from reactions of 15a and 15b with crotylboronates 10 and 11; the fourth isomer, 32a, is available with 83% selectivity. Chiral reagents 9-11 thus appear well suited for application to complex problems in organic synthesis.
• Highly Diastereo- and Enantioselective Reagents for Aldehyde Crotylation
  作者：Blaine M. Hackman、Pamela J. Lombardi、James L. Leighton

  DOI：10.1021/ol0480731

  日期：2004.11.1

  Two new, crystalline solid, storable, and highly enantioselective reagents for aldehyde crotylation have been developed. Both (cis and trans) crotylsilane reagents are easily prepared in bulk, require trivial reaction conditions, and provide the homoallylic alcohol products with near diastereo- and enantiospecificity in many cases.
• Asymmetric synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: preparation of the chiral crotylboronates and reactions with achiral aldehydes
  作者：William R. Roush、Kaori Ando、Daniel B. Powers、Alan D. Palkowitz、Ronald L. Halterman

  DOI：10.1021/ja00173a023

  日期：1990.8

  Crotylboronates undergo highly diastereo- and enantioselective reactions with aliphatic (linear or α-monobranched; 72-91% ee), aromatic and α,β-unsaturated aldehydes (55-74% ee). The reaction diastereoselectivity closely parallels the reagent isomeric purity especially for reactions performed at −78 o C. The enantioselectivity is best in toluene for all substrates except benzaldehyde where best results

  巴豆基硼酸酯与脂肪族（线性或 α-单支链；72-91% ee）、芳香族和 α,β-不饱和醛（55-74% ee）发生高度非对映选择性和对映选择性反应。反应的非对映选择性与试剂异构体纯度密切相关，特别是对于在 -78 o C 下进行的反应。对所有底物的对映选择性在甲苯中最佳，但苯甲醛除外，因为苯甲醛在 THF 中获得最佳结果。本研究中合成的 14 种高烯丙醇中有 9 种的相对和绝对立体化学是通过与 Sharpless 不对称环氧化制备的环氧醇的相关性来确定的