2,3-dimethyl-1-phenylbut-3-en-1-ol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3-dimethyl-1-phenylbut-3-en-1-ol
• 英文别名: 2,3-dimethyl-1-phenyl-3-buten-1-ol
• 化学式: C₁₂H₁₆O
• 分子量: 176.258
• InChiKey: HDCNWWBNSUZFHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  2,3-dimethyl-1-phenylbut-3-en-1-ol 在 Jones reagent 作用下， 以 乙醚 为溶剂， 生成 1-phenyl-2,3-dimethyl-3-buten-1-one
  参考文献：
  名称：

  Palladium-Catalyzed Oxime Assisted Intramolecular Dioxygenation of Alkenes with 1 atm of Air as the Sole Oxidant

  摘要：

  This paper describes a palladium-catalyzed oxime assisted intramolecular dioxygenation of alkenes by using 1 atm of air as the sole oxidant under extremely mild conditions, which demonstrated the feasibility of incorporating atmospheric oxygen into synthetically useful products under 1 atm of air at room temperature.

  DOI：

  10.1021/ja100716x
• 作为产物：
  描述：

  1-(trimethylsilyl)-2-methyl-2-butene 在 三氟化硼四氢呋喃络合物 、 (2R,3R)-2-O-(2,6-diisopropoxybenzoyl)tartaric acid 、 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 生成 2,3-dimethyl-1-phenylbut-3-en-1-ol
  参考文献：
  名称：

  Catalytic asymmetric allylation using a chiral (acyloxy)borane complex as a versatile Lewis acid catalyst

  摘要：

  In the presence of 20 mol % of a chiral (acyloxy)borane (CAB) complex prepared from (2R,3R)-2-O-(2,6-diisopropoxybenzoyl)tartaric acid and borane-tetrahydrofuran, various allyltrimethylsilanes react with achiral aldehydes to afford the corresponding homoallylic alcohols in good yields with high diastereo- and enantioselectivities. Furthermore, the reactivity of allylation can be improved without reducing the enantioselelctivity by using 10-20 mol % of the CAB complex prepared from 3,5-bis(trifluoromethyl)phenylboronic acid and chiral tartaric acid derivative. The observed selectivities and re-face attack of nucleophiles on the carbonyl carbons of aldehydes imply that the extended transition-state model is applicable.

  DOI：

  10.1021/ja00077a054

文献信息

• Titanium-Catalyzed Hydroalumination of Conjugated Dienes: Access to Fulvene-Derived Allylaluminium Reagents and Their Diastereoselective Reactions with Carbonyl Compounds
  作者：Jomy Joseph、Florian Jaroschik、Dominique Harakat、K. V. Radhakrishnan、Jean-Luc Vasse、Jan Szymoniak

  DOI：10.1002/chem.201304775

  日期：2014.4.25

  The described titanium‐catalyzed hydroalumination of conjugated dienes opens up a new way to allylaluminium reagents. The reaction is carried out by using diisobutylaluminium hydride (DIBAL‐H) and a catalytic amount of [Cp2TiCl2] (Cp=cyclopentadienyl). When applied to mono‐ and disubstitued pentafulvenes, this reaction proceeds in a highly endocyclic manner. The formed allylaluminium compounds react

  钛催化的共轭二烯加氢铝化为烯丙基铝试剂开辟了一条新途径。通过使用氢化二异丁基铝（DIBAL-H）和催化量的[Cp 2 TiCl 2]（Cp ＝环戊二烯基）。当将其用于单和五元五联戊酸酯时，该反应会以高度内环的方式进行。形成的烯丙基铝化合物与醛和酮发生区域和立体选择性反应，生成均聚烯丙醇，适合作为功能化环戊酮的合成子。还研究了这种方法对简单二烯的扩展。在提出的机理中，最初形成的双金属物种（Ti / Al）参与了两个可能的催化循环，这些循环包括直接加氢铝化或/和加氢钛化，然后进行钛到铝的金属转移。
• Generation of Allylic Indium by Hydroindation of 1,3-Dienes and One-Pot Reaction with Carbonyl Compounds
  作者：Naoki Hayashi、Hiroyuki Honda、Makoto Yasuda、Ikuya Shibata、Akio Baba

  DOI：10.1021/ol061797n

  日期：2006.9.1

  A hydroindation of 1,3-dienes by dichloroindium hydride (HInCl2) generates allylic indiums that react with carbonyl or imine moieties in a one-pot treatment. The former reaction proceeds in a radical manner, and the latter is ionic allylation. Moreover, both reactions require no additives such as radical initiators, Lewis acids, or transition metal catalysts.

  通过二氯氢化铟（HInCl2）对1,3-二烯进行加氢精制会生成烯丙基铟，它们在一键处理中会与羰基或亚胺基反应。前者以自由基方式进行，后者是离子烯丙基化。而且，两个反应都不需要添加剂，例如自由基引发剂，路易斯酸或过渡金属催化剂。
• Z-Selective Synthesis of Homoallylic Alcohols<i>via</i>2-Alkenylation of Aldehydes by 1-(Tributylstannyl)-2-alkene
  作者：Hideyoshi Miyake、Kimiaki Yamamura

  DOI：10.1246/cl.1994.897

  日期：1994.5

  1-(Tributylstannyl)-2-alkene reacts with a solution of an aldehyde and BuSnCl3 to give (Z)-homoallylic alcohol. Z-Selective 2-methyl-2-butenylation can be accomplished by using (Z)-2-methyl-1-(tributylstannyl)-2-butene instead of 1-(tributylstannyl)-2-alkene. This reaction is useful as a new method to make (Z)-double bond. An application of the present method for a synthesis of pheromones is also described.

  1-(三丁基锡基)-2-烯与醛的溶液和BuSnCl3反应生成（Z）-同烯醇。通过使用（Z）-2-甲基-1-(三丁基锡基)-2-丁烯代替1-(三丁基锡基)-2-烯，可以实现Z选择性2-甲基-2-丁烯化。这种反应作为制备（Z）-双键的新方法非常有用。本文还描述了该方法在合成信息素中的应用。
• Ruthenium-Catalyzed C−C Bond Forming Transfer Hydrogenation: Carbonyl Allylation from the Alcohol or Aldehyde Oxidation Level Employing Acyclic 1,3-Dienes as Surrogates to Preformed Allyl Metal Reagents
  作者：Fumitoshi Shibahara、John F. Bower、Michael J. Krische

  DOI：10.1021/ja801213x

  日期：2008.5.1

  Under the conditions of ruthenium-catalyzed transfer hydrogenation, commercially available acyclic 1,3-dienes, butadiene, isoprene, and 2,3-dimethylbutadiene, couple to benzylic alcohols 1a-6a to furnish products of carbonyl crotylation 1b-6b, carbonyl isoprenylation 1c-6c, and carbonyl reverse 2-methyl prenylation 1d-6d. Under related transfer hydrogenation conditions employing isopropanol as terminal

  市售无环1,3-二烯、丁二烯、异戊二烯、2,3-二甲基丁二烯在钌催化转移氢化条件下与苄醇1a-6a偶联，得到羰基巴豆酰化产物1b-6b、羰基异戊二烯化产物1c -6c，和羰基反向2-甲基异戊二烯化1d-6d。在使用异丙醇作为末端还原剂的相关转移氢化条件下，异戊二烯与醛7a-9a偶联，提供相同的羰基异戊二烯化1c-3c产物。因此，在不存在预先形成的烯丙基金属试剂的情况下，由醇或醛的氧化水平实现羰基烯丙基化。还证明了与脂肪醇（异戊二烯至 1-壬醇，分离产率 65%）和烯丙醇（异戊二烯至香叶醇，分离产率 75%）的偶联。同位素标记研究证实了一种涉及反应物醇或牺牲醇 (i-PrOH) 供氢的机制。
• First catalytic allyltitanation reactions
  作者：Laurianne Bareille、Pierre Le Gendre、Claude Moïse

  DOI：10.1039/b414322a

  日期：——

  Catalytic allyltitanation reactions were accomplished from dienes and aldehydes with only 5% of titanocene complexes at the expense of employing stoichiometric amounts of PMHS.

  在二烯和醛类反应中，只需使用5%的二茂钛配合物，即可完成催化烯丙基钛化