2,2-二甲基-4-亚甲基-5-己烯-3-醇 | 100281-11-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2,2-二甲基-4-亚甲基-5-己烯-3-醇
• 英文名称: 2,2-methyl-4-methylene-5-hexen-3-ol
• 英文别名: 2,2-dimethyl-4-methylene-5-hexen-3-ol；2,2-dimethyl-4-methylidenehex-5-en-3-ol
• CAS: 100281-11-6
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: QEASBMGTHNRMCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.14
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  20.23
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  2,2-二甲基-4-亚甲基-5-己烯-3-醇 生成 (2,2-dimethyl-4-methylidenehex-5-en-3-yl) 4-nitrobenzoate
  参考文献：
  名称：

  WADA, EIJI;KANEMASA, SHUJI;FUJIWARA, ISAMU;TSUGE, OTOHIKO, BULL. CHEM. SOC. JAP., 1985, 58, N 7, 1942-1945

  摘要：

  DOI：
• 作为产物：
  描述：

  diisopropyl 2,3-butadien-1-ylboronate 以60%的产率得到
  参考文献：
  名称：

  Soundararajan Raman, Li Guisheng, Brown Herbert C., Tetrahedron Lett, 36 (1995) N 14, S 244-2444

  摘要：

  DOI：

文献信息

• A Convenient Route to 2-Lithio-1,3-butadiene from Chloroprene<i>via</i>2-Stannyl-1,3-butadiene
  作者：Eiji Wada、Shuji Kanemasa、Isamu Fujiwara、Otohiko Tsuge

  DOI：10.1246/bcsj.58.1942

  日期：1985.7

  A convenient route to 2-lithio-1,3-butadiene from chloroprene via a 2-stannyl-1,3-butadiene is presented, and the regioselecdve additions to a variety of carbonyl groups are demonstrated.

  提出了通过 2-甲锡烷基-1,3-丁二烯从氯丁二烯制备 2-锂硫-1,3-丁二烯的便捷途径，并证明了区域选择性加成到各种羰基。
• Racemic and diastereoselective synthesis of alkyl(1,3-butadien-2-yl)methanols via a novel homoallenylboration of aldehydes with diisopropyl 2,3-butadien-1-ylboronate
  作者：Raman Soundararajan、Guisheng Li、Herbert C. Brown

  DOI：10.1016/0040-4039(95)00311-y

  日期：1995.4

  3-butadien-1-ylboronate has been prepared by a simple method and its utility as a novel homoallenylborating reagent has been demonstrated with a series of aldehydes. Also, a high diastereoselectivity of this reagent in its reaction with an α-chiral aldehyde has been established.

  已经通过简单的方法制备了2，3-丁二烯-1-基硼酸二异丙酯，并且已经证明了其作为新型的均烯丙基硼酸酯化试剂的用途，并带有一系列的醛。而且，已经确定了该试剂在与α-手性醛的反应中的高非对映选择性。
• 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.