(-)-(2S)-2-(4-nitrophenyl)-4-penten-2-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: (-)-(2S)-2-(4-nitrophenyl)-4-penten-2-ol
• 英文别名: (S)-(-)-2-(4-nitrophenyl)-pent-4-en-2-ol；(S)-(-)-2-(4-nitrophenyl)pent-4-en-2-ol；(2S)-2-(4-nitrophenyl)pent-4-en-2-ol
• 化学式: C₁₁H₁₃NO₃
• 分子量: 207.229
• InChiKey: UFDMLJUFIVZOGT-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  对硝基苯乙酮 以 四氢呋喃 、 正己烷 为溶剂， 反应 9.0h， 生成 (-)-(2S)-2-(4-nitrophenyl)-4-penten-2-ol
  参考文献：
  名称：

  B-Allyl-10-Ph-9-borabicyclo[3.3.2]decanes：为酮的不对称烯丙基硼化而设计的策略

  摘要：

  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，

  DOI：

  10.1021/ja053865r

文献信息

• The Mechanism and an Improved Asymmetric Allylboration of Ketones Catalyzed by Chiral Biphenols
  作者：David S. Barnett、Philip N. Moquist、Scott E. Schaus

  DOI：10.1002/anie.200904715

  日期：2009.11.2

  Giving it a boost: A mechanistic study of the enantioselective asymmetric titled reaction with allyldiisopropoxyborane catalyzed by chiral biphenols revealed a key ligand exchange process which liberates isopropyl alcohol. The addition of iPrOH to the reaction increases the overall rate and enantioselectivity. As a result an improved reaction, employing allyldioxaborinane with 1 and tBuOH, resulted

  给它一个推动：对由手性双酚催化的烯丙基二异丙氧基硼烷的对映选择性不对称标题反应的机理研究揭示了一个关键的配体交换过程，它释放了异丙醇。向反应中加入i PrOH 提高了总速率和对映选择性。因此，使用烯丙基二氧硼烷与1和t BuOH的改进反应导致高产物产率和对映选择性。
• On the use of mixtures of organotin species for catalytic enantioselective ketone allylation—a detective story
  作者：Anthony Cunningham、Vijaya Mokal-Parekh、Claire Wilson、Simon Woodward

  DOI：10.1039/b313384b

  日期：——

  In the presence of enantiopure MTBH2 (monothiobinaphthol, 2-hydroxy-2′mercapto-1,1′-binaphthyl; 0.2 eq.) quantitative allylation of ArC(O)Me takes place with impure Sn(CH2CHCH2)4 (prepared from allyl chloride, air-oxidised magnesium and SnCl4) to yield tert-homoallylic alcohols in 85–92% ee. In the same process highly purified, or commercial, Sn(CH2CHCH2)4 yields material of only 35–50% ee. The origin of these effects is the presence of small amounts of the compounds, EtSn(CH2CHCH2)3, ClSn(CH2CHCH2)3 ClSnEt(CH2CHCH2)2 in the tetraallyltin sample and the presence of traces of water (which inhibits achiral background reactions). All the triallyl and diallyl species enhance the stereoselectivity in the catalytic allylation reaction, the chlorides more so than the ethyl compound. Hydrolysis of ClSnEt(CH2CHCH2)2 affords crystallographically characterised Sn4(μ3-O)(μ2-Cl)2Cl2Et4(CH2CHCH2)4. Reaction of this latter compound with MTBH2 leads to the most potent catalyst.

  在手性纯MTBH2（单硫代苯二醇，2-羟基-2′-巯基-1,1′-联萘；0.2当量）的存在下，与不纯的Sn(CH2CHCH2)4（由丙烯氯、空气氧化镁和SnCl4制备）进行定量的烯丙基化反应，能够生成含有85–92%光学纯度的叔同烯丙醇。在同一过程中，高度纯化的或商业化的Sn(CH2CHCH2)4仅产生35–50%的光学纯度。这些效果的来源是四丙基锡样品中存在少量化合物EtSn(CH2CHCH2)3、ClSn(CH2CHCH2)3以及ClSnEt(CH2CHCH2)2，以及水的微量存在（抑制了非手性背景反应）。所有的三烯丙基和二烯丙基物种都增强了催化烯丙基化反应中的立体选择性，其中氯化物的效果优于乙基化合物。ClSnEt(CH2CHCH2)2的水解反应生成了具有晶体结构特征的Sn4(μ3-O)(μ2-Cl)2Cl2Et4(CH2CHCH2)4。后者与MTBH2的反应生成了最强的催化剂。
• Highly Enantioselective Catalytic Ketone Allylation with Sn(CH2CH=CH2)4/RSn(CH2CH=CH2)3 Mixtures (R = Et, Bu)
  作者：Anthony Cunningham、Simon Woodward

  DOI：10.1055/s-2002-19323

  日期：——

  In the presence of the monothiobinaphthol (MTB) ligand aryl ketones are allylated by mixtures of Sn(CH2CH=CH2)4/RSn(CH2CH=CH2)3 (R = Et, Bu) in high e.e. The presence of water suppresses racemic background allylation.

  在单硫代萘酚 (MTB) 配体存在的情况下，芳基酮可通过 Sn(CH2CH=CH2)4/RSn(CH2CH=CH2)3 (R = Et, Bu) 的混合物在高浓度 e.e. 条件下发生烯丙基化反应。
• Enantioselective catalytic allylation of arylmethylketones using tetraallyltin and tin(IV) chloride mixtures
  作者：Oscar Prieto、Simon Woodward

  DOI：10.1016/j.jorganchem.2005.11.017

  日期：2006.4

  Reaction of SnCl4 with Sn(CH2CH=CH2)(4) in the presence of water and monothiobinaphthol [2,2'-C20H12(OH)(SH)] allows the formation of a selective catalyst for the allylation of ketones (up to 94% e.e.). (c) 2005 Elsevier B.V. All rights reserved.
• Experimental and theoretical investigation of the scope of enantioselective ketone allylations employing Nakamura’s allylzinc–bisoxazoline reagent
  作者：A. George Johnson、Brad M. Loertscher、Adam R. Moeck、Sam S. Matthews、Daniel H. Ess、Steven L. Castle

  DOI：10.1016/j.bmcl.2010.11.121

  日期：2011.5

  The scope of enantioselective allylations employing Nakamura's allylzinc-bisoxazoline reagent was examined by performing allylations of a selection of readily available ketones. Low-to-moderate ee's were observed, and a computational study was conducted to rationalize the results. Examination of transition structures of previously performed allylations that proceeded with high ee revealed the importance of both local and global control elements in these successful reactions. The ability of density functional theory methods to estimate the enantioselectivity of these asymmetric ketone allylations was established. All allylations that were studied computationally exhibited low (<5 kcal/mol) activation barriers, a result that is consistent with the highly reactive nature of Nakamura's reagent. (C) 2010 Elsevier Ltd. All rights reserved.