(-)-(3S)-2,3-dimethylhexa-5-en-3-ol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(3S)-2,3-dimethylhexa-5-en-3-ol
• 英文别名: 2,3-dimethylhex-5-en-3-ol；(3S)-2,3-dimethylhex-5-en-3-ol
• 化学式: C₈H₁₆O
• 分子量: 128.214
• InChiKey: YGYJSFXFOXFEOD-QMMMGPOBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  在 氨 、 sodium 作用下， 生成 (+)-(3R)-2,3-dimethylhexa-5-en-3-ol 、 (-)-(3S)-2,3-dimethylhexa-5-en-3-ol
  参考文献：
  名称：

  Enantioselective Synthesis of Tertiary Homoallylic Alcohols via Diastereoselective Addition of Allylsilanes to Ketones

  摘要：

  DOI：

  10.1021/ja00126a025

文献信息

• A Spirocyclic Chiral Borate for Catalytic Enantioselective Nozaki-Hiyama Allylation of Ketones
  作者：Xin-Ren Huang、Chinpiao Chen、Gene-Hsian Lee、Shie-Ming Peng

  DOI：10.1002/adsc.200900595

  日期：2009.12

  A new class of chiral spirocyclic borate ligands 5a–d with a rigid borocycle has been developed. The catalyst formed from chromium(II)-5a promotes the highly efficient enantioselective Nozaki–Hiyama allylation of alkyl and aryl ketones using allyl bromide. The scope of the present method is shown to be wide, and it affords an efficient access to chiral tertiary homoallylic alcohols.

  已经开发出一类新的具有刚性硼环的手性螺环硼酸盐配体5a-d。由铬（II）-5a形成的催化剂可使用烯丙基溴促进烷基和芳基酮的高效对映选择性Nozaki-Hiyama烯丙基化。已显示本方法的范围很广，并且它提供了有效的手性叔均烯丙基醇的获得途径。
• <i>B</i>-Allyl-10-Ph-9-borabicyclo[3.3.2]decanes:  Strategically Designed for the Asymmetric Allylboration of Ketones
  作者：Eda Canales、K. Ganeshwar Prasad、John A. Soderquist

  DOI：10.1021/ja053865r

  日期：2005.8.24

  bicyclic structure. In addition to providing the homoallylic alcohols 6 efficiently (70-92%), the procedure also permits the efficient recovery of the chiral boron moiety (67-82%) as an air-stable crystalline N-methylpseudoephedrine complex 4 for the direct regeneration of 1 with allylmagnesium bromide in ether (98%). The reagent gives predictable stereochemistry, providing a strategically designed "chiral

  报道了两种对映体形式的 B-烯丙基-10-(苯基)-9-硼双环 [3.3.2] 癸烷 (1) 的简单有效合成。当该过程在 0 摄氏度进行时，这些试剂在 -78 摄氏度烯丙基硼化过程中的显着对映选择性 (81-99% ee) 仅适度减弱，这种现象归因于其刚性双环结构。除了有效地提供高烯丙醇 6 (70-92%)，该程序还允许有效回收手性硼部分 (67-82%) 作为空气稳定的结晶 N-甲基伪麻黄碱复合物 4，用于直接再生1 与乙醚中的烯丙基溴化镁 (98%)。该试剂提供可预测的立体化学，提供一个战略性设计的“手性口袋”，特别容易接受领先的甲基（例如，
• Synthesis of Enantiopure Homoallylic Alcohols
  作者：Lutz F. Tietze、Kai Schiemann、Christoph Wegner、Christian Wulff

  DOI：10.1002/(sici)1521-3765(19980904)4:9<1862::aid-chem1862>3.0.co;2-c

  日期：1998.9.4

  A highly selective asymmetric domino allylation of aliphatic ketones is described. When methyl ketones 1a-g, the chiral trimethylsilyl ether 2, and allylsilane 3 react in the presence of catalytic amounts of trifluoromethanesulfonic acid, the homoallylic ethers 4a-g are produced with up to 24:1 diastereoselectivity and 89% yield. Cleavage of the obtained tertiary homoallylic ethers C using lithium or sodium in liquid ammonia gives the homoallytic alcohols 5 in 75 to 95% yield and up to 92% ee. Even ethyl methyl ketone 1a, the most difficult example, showed a stereoselectivity of 9:1 at -78 degrees C and 24:1 at -109 degrees C. In addition, the allylation of protected hydroxyalkyl methyl ketones 7a-j was investigated to give the corresponding homoallylic ethers 8a-j with a diastereoselectivity of up to >24:1 and 98% yield. In contrast, ethyl alkyl ketones 1h-j have a low selectivity.