(S)-cyclohexyl(1,3-butadien-2-yl)methanol | 173398-01-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-cyclohexyl(1,3-butadien-2-yl)methanol
• 英文别名: (S)-1-cyclohexyl-2-methylenebut-3-en-1-ol；(1S)-1-cyclohexyl-2-methylidenebut-3-en-1-ol
• CAS: 173398-01-1
• 化学式: C₁₁H₁₈O
• 分子量: 166.263
• InChiKey: CBPKITKNRGSKPI-LLVKDONJSA-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：

  环己烷基甲醛 在 (11bS)-4-羟基-2,6-二[2,4,6-三(异丙基)苯基]-二萘并[2,1-d:1',2'-f][1,3,2]二氧杂磷杂卓4-氧化物 作用下， 以 四氯化碳 为溶剂， 反应 24.0h， 以92%的产率得到(S)-cyclohexyl(1,3-butadien-2-yl)methanol
  参考文献：
  名称：

  一种手性1,3-丁二烯-2-仲醇的制备方法

  摘要：

  本发明涉及手性1,3‑丁二烯‑2‑仲醇的制备方法，其通过手性磷酸催化高联烯基硼酸酯与醛的对映选择性加成反应，制备得到手性1,3‑丁二烯‑2‑仲醇类化合物，其反应通式如下：式中：R为芳基或烷基。本发明的有益效果在于：通过本发明制备所得的手性1,3‑丁二烯‑2‑仲醇类化合物，为以后手性药物和天然产物的合成奠定基础。

  公开号：

  CN104788274B

文献信息

• Asymmetric Synthesis of 1,3-Butadienyl-2-carbinols by the Homoallenylboration of Aldehydes with a Chiral Phosphoric Acid Catalyst
  作者：Yiyong Huang、Xing Yang、Zongchao Lv、Chen Cai、Cheng Kai、Yong Pei、Yu Feng

  DOI：10.1002/anie.201501832

  日期：2015.6.15

  Asymmetric C(sp)C(sp2) bond formation to give enantiomerically enriched 1,3‐butadienyl‐2‐carbinols occurred through a homoallenylboration reaction between a 2,3‐dienylboronic ester and aldehydes under the catalysis of a chiral phosphoric acid (CPA). A diverse range of enantiomerically enriched butadiene‐substituted secondary alcohols with aryl, heterocyclic, and aliphatic substituents were synthesized

  不对称 C(sp)  C(sp 2) 在手性磷酸 (CPA) 的催化下，通过 2,3-二烯基硼酸酯和醛之间的均烯基硼化反应形成对映异构体富集的 1,3-丁二烯基-2-甲醇。以非常高的收率和高对映选择性合成了多种具有芳基、杂环和脂肪族取代基的富含对映异构体的丁二烯取代的仲醇。初步的密度泛函理论 (DFT) 计算表明，反应通过环状六元椅状过渡态进行，在丙二烯试剂中具有必要的氢键活化。该催化反应适用于手性烷基丁二烯基加合物的克级合成，
• Preparation of racemic and chiral alkyl(1,3-butadien-2-yl)methanol derivatives utilizing 1-trimethylsilyl-2,3-butadiene as a diene source
  作者：Susumi Hatakeyama、Kazutoshi Sugawara、Mitsuhiro Kawamura、Seiichi Takano

  DOI：10.1016/0040-4039(91)80026-3

  日期：1991.1

  examined establishing an efficient method for the preparation of alkyl(1,3-butadien-2-yl)methanols. Application of this method to chiral acetals prepared from (R,R)-2,4-pentanediol led to chiral alkyl(1,3-butadien-2-yl)methanol derivatives with high optical purity which were alternatively synthesized by the Sharpless kinetic resolution of racemic alkyl(1,3-butadien-2-yl)methanols.

  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。
• 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.