(-)-(S)-3,5-dimethyl-1-phenyl-1,5-hexadien-3-ol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (-)-(S)-3,5-dimethyl-1-phenyl-1,5-hexadien-3-ol
• 英文别名: (S,E)-3,5-dimethyl-1-phenylhexa-1,5-dien-3-ol；3,5-dimethyl-1-phenyl-hexa-1,5-dien-3-ol；(1E,3S)-3,5-dimethyl-1-phenylhexa-1,5-dien-3-ol
• 化学式: C₁₄H₁₈O
• 分子量: 202.296
• InChiKey: YQHAXGLXYYUHRY-ATWMFIQVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  四(2-甲基丙-2-烯基)锡烷 、 苄叉丙酮 在 titanium(IV) isopropylate 、 (R)-5,5',6,6',7,7',8,8'-八氢-[1,1'-联萘]-2,2'-二酚 异丙醇 作用下， 以 乙腈 为溶剂， 反应 18.0h， 生成 (+)-(R)-3,5-dimethyl-1-phenyl-1,5-hexadien-3-ol 、 (-)-(S)-3,5-dimethyl-1-phenyl-1,5-hexadien-3-ol
  参考文献：
  名称：

  Catalytic Asymmetric Methallylation of Ketones with an (H₈-BINOLate)Ti-Based Catalyst

  摘要：

  The first catalytic asymmetric methallylation of ketones is reported. The catalyst, which is generated from titanium tetraisopropoxide, H-8-BINOL, 2-propanol, and tetramethallylstannane, reacts with ketones in acetonitrile to afford tertiary homoallylic alcohols in fair to excellent yields (55-99%) and fair to high enantioselectivities (46-90%). Ozonolysis of the resulting products provides access to chiral, ss-hydroxy ketones, which are not readily prepared from direct asymmetric aldol reaction of acetone with ketones.

  DOI：

  10.1021/ol061417y

文献信息

• Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and α-Ketoesters
  作者：Daniel W. Robbins、KyungA Lee、Daniel L. Silverio、Alexey Volkov、Sebastian Torker、Amir H. Hoveyda

  DOI：10.1002/anie.201603894

  日期：2016.8.8

  catalytic additions of easy‐to‐handle allyl‐B(pin) (pin=pinacolato) compounds to ketones and acyclic α‐ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small‐molecule aminophenol‐based catalysts. Notably, with ketones, increasing

  开发了一套广泛适用的方法，用于将易于处理的烯丙基-B（pin）（pin = pinacolato）化合物有效催化加成到酮和无环α-酮酸酯中。因此，可以以60至> 98％的产率和高达99：1的对映体比例获得各种各样的叔醇。这一发展的核心是合理改变小分子氨基酚基催化剂的结构。明显地，对于酮，增加催化剂部分的尺寸（tBu至SiPh 3）导致更高的对映选择性。另一方面，对于α-酮酸酯，不仅如此，因为Me取代会导致对映选择性大大提高，而且选择性的意义也相反。
• Asymmetric Synthesis of 2°- and 3°-Carbinols via <i>B</i>-Methallyl-10-(TMS and Ph)-9-borabicyclo[3.3.2]decanes
  作者：José G. Román、John A. Soderquist

  DOI：10.1021/jo701633k

  日期：2007.12.1

  [GRAPHICS]Simple Grignard procedures provide methallylboranes la and 1b in enantiomerically pure form from air-stable precursors in 98% and 95% yields, respectively. These reagents add smoothly to aldehydes and methyl ketones, respectively, providing branched 2 degrees- (6, 69-89%, 94-99% ee) and 3 degrees-(10, 71-87%, 74-96% ee) homoallylic alcohols.