(R)-cyclohexyl(1,3-butadien-2-yl)methanol | 137104-11-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-cyclohexyl(1,3-butadien-2-yl)methanol
• 英文别名: (R)-1-cyclohexyl-2-methylenebut-3-en-1-ol；(1R)-1-cyclohexyl-2-methylidenebut-3-en-1-ol
• CAS: 137104-11-1
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: CBPKITKNRGSKPI-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  (4R,6R)-2-Cyclohexyl-4,6-dimethyl-[1,3]dioxane 在 sodium hydroxide 、 6TiCl₄*5Ti(OⁱPr)4 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 生成 (R)-cyclohexyl(1,3-butadien-2-yl)methanol
  参考文献：
  名称：

  以1-三甲基甲硅烷基-2,3-丁二烯为二烯源制备外消旋和手性烷基（1,3-丁二烯-2-基）甲醇衍生物

  摘要：

  已经研究了Ti（IV）氯化钛介导的1-三甲基甲硅烷基-2,3-丁二烯与各种醛和缩醛的反应，建立了制备烷基（1,3-丁二烯-2-基）甲醇的有效方法。该方法在由（R，R）-2,4-戊二醇制得的手性缩醛中的应用可生成具有高光学纯度的手性烷基（1,3-丁二烯-2-基）甲醇衍生物，可以通过Sharpless动力学拆分合成外消旋的烷基（1,3-丁二烯-2-基）甲醇。

  DOI：

  10.1016/0040-4039(91)80026-3

文献信息

• Enantioselective synthesis of butadien-2-ylcarbinols via (silylmethyl)allenic alcohols from chromium-catalyzed additions to aldehydes utilizing chiral carbazole ligands
  作者：María Durán-Galván、Shilpa A. Worlikar、Brian T. Connell

  DOI：10.1016/j.tet.2010.07.065

  日期：2010.9

  alcohols are obtained by treatment of aldehydes with (4-bromobut-2-ynyl)trimethylsilane in the presence of a catalytic amount of CrCl3 or CrCl2. Several new tridentate bis(oxazolinyl)carbazole ligands were synthesized and evaluated as the source of chirality. The synthesis of chiral allenic alcohols can be achieved in good yields (58–88%) and enantioselectivities (55–78% ee). Allenic alcohols may be

  描述了通过使用中间体（三甲基甲硅烷基）甲基烯丙醇来合成手性，非外消旋丁二烯基羰基醇。通过在催化量的CrCl 3或CrCl 2存在下用（4-溴丁-2-炔基）三甲基硅烷处理醛来获得烯丙醇。合成了几种新的三齿双（恶唑啉基）咔唑配体，并将其评估为手性来源。手性烯丙醇的合成可以实现良好的收率（58-88％）和对映选择性（55-78％ee）。可用TBAF或2 M HCl处理烯丙醇，以43-86％的收率提供所需的二烯。或者，当用N-碘代琥珀酰亚胺处理时，（三甲基甲硅烷基）甲基烯丙醇提供碘丁二烯基甲醇。
• Asymmetric Synthesis of (1,3-Butadien-2-yl)methanols from Aldehydes via [1-(Silylmethyl)allenyl]methanols
  作者：María Durán-Galván、Brian T. Connell

  DOI：10.1002/ejoc.201000199

  日期：2010.5

  [1-(Silylmethyl)allenyl]methanols 2 were efficiently synthesized from aldehydes and (4-bromobut-2-ynyl)trimethylsilane in the presence of a catalytic amount of CrCl 2 and tridentate carbazole ligands. The desired compounds were obtained with good yields (43-88%) and enantioselectivities (55-78 % ee). Alcohols 2 may be treated with TBAF or 2 M HCl in the case of aliphatic substrates, to provide (1,

  在催化量的 CrCl 2 和三齿咔唑配体存在下，[1-(甲硅烷基甲基)烯基]甲醇 2 由醛和 (4-溴丁-2-炔基)三甲基硅烷有效合成。以良好的产率 (43-88%) 和对映选择性 (55-78% ee) 获得所需化合物。在脂肪族底物的情况下，醇2可以用TBAF或2M HCl处理，以43-81％的产率提供(1,3-丁二烯-2-基)甲醇3。这种方法允许合成二烯 3 没有区域选择性问题，并且它可以容忍大量的功能。
• Chiral Synthesis <i>via</i> Organoboranes. 44. Racemic and Diastereo- and Enantioselective Homoallenylboration Using Dialkyl 2,3-Butadien-1-ylboronate Reagents. Another Novel Application of the Tandem Homologation−Allylboration Strategy
  作者：Raman Soundararajan、Guisheng Li、Herbert C. Brown

  DOI：10.1021/jo9513976

  日期：1996.1.1

  A highly general and efficient racemic and diastereo- and enantioselective homoallenylboration has been achieved with a novel boron reagent, dialkyl 2,3-butadien-1-ylboronate (dialkyl homoallenylboronate). The starting diisopropyl 2,3-butadien-1-ylboronate is prepared from allenylmagnesium bromide and diisopropyl (halomethyl)boronate. This beta,gamma-unsaturated boronate reagent reacts readily with aldehydes via the usual allylic rearrangement to give the alkyl(1,3-butadien-2-yl)methanols in excellent yield. Among the solvents examined, toluene favored enhanced reaction rates. The reaction is relatively sensitive to steric effects, so that sterically hindered aldehydes react significantly slower. Generally, the reactivities are moderately lower than those of the corresponding simple allylboronates, possibly due to the reduced HOMO electron density of the internal double bond. Also, the reagent exhibits a unique anti diastereoselectivity in reaction with alpha-chiral aldehydes in contrast to the syn selectivity observed with a corresponding organosilicon reagent. However, this anti selectivity is similar to that observed for the allylboration reactions. We have successfully extended this reaction to the first general synthesis of optically active alkyl(1,3-butadien-2-yl)methanols using chiral tartrate boronate reagents with diisopropyl tartrate (DIPT) and bis(2,4-dimethyl-3-pentyl) tartrate (DMPT) as the chiral modifiers. These reagents react with aldehydes even at -78 degrees C, albeit slowly, and exhibit remarkable enantioselectivity with all classes of aldehydes examined with the exception of aromatic and alpha-alkoxy aldehydes. Again, while the selectivity parallels that of the corresponding allylboronate, the reactivities are lower. Also, the double asymmetric homoallenylboration of 2,3-O-isopropylidene-D-glyceraldehyde using the DMPT modified boronate reagent gives an excellent 98.5% anti selectivity in the matched case and a moderately lower value, 82% syn selectivity, in the mismatched case.