(2R,3E)-4-(4-methylphenyl)-3-buten-2-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: (2R,3E)-4-(4-methylphenyl)-3-buten-2-ol
• 英文别名: (R,E)- 4-(4'-methylphenyl)but-3-en-2-ol；(E,2R)-4-(4-methylphenyl)but-3-en-2-ol
• 化学式: C₁₁H₁₄O
• 分子量: 162.232
• InChiKey: FQBWGGNZOFDJAD-VHODGJRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 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：

  (2R,3E)-4-(4-methylphenyl)-3-buten-2-ol 在 4-二甲氨基吡啶 、 bis(1,5-cyclooctadiene)nickel (0) 、 sodium methylate 、 三乙胺 、 苄基二苯膦 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 19.0h， 生成 (S,E)-4,4'-(but-1-ene-1,3-diyl)bis(chlorobenzene)
  参考文献：
  名称：

  Enantiospecific, Nickel-Catalyzed Cross-Couplings of Allylic Pivalates and Arylboroxines

  摘要：

  We have developed an enantiospecific, nickel-catalyzed cross-coupling of unsymmetric 1,3-disubstituted allylic pivalates with arylboroxines. The success of this reaction relies on the use of BnPPh2 as a supporting ligand for the nickel(0) catalyst and NaOMe as a base. This method shows excellent functional group tolerance and broad scope in both the allylic pivalate and arylboroxine, enabling the preparation of 1,3-diaryl allylic products in high yields with excellent levels of regioselectivity and stereochemical fidelity.

  DOI：

  10.1021/ol5016724
• 作为产物：
  描述：

  (E)-4-(p-tolyl)but-3-en-2-ol 在 Candida parapsilosis ATCC 7330 whole cells 作用下， 以 乙醇 、 水 为溶剂， 反应 3.0h， 以72%的产率得到(2R,3E)-4-(4-methylphenyl)-3-buten-2-ol
  参考文献：
  名称：

  Enantiomerically pure allylic alcohols: preparation by Candida parapsilosis ATCC 7330 mediated deracemisation

  摘要：

  Biocatalytic deracemisation of racemic allylic alcohols by whole cells of Candida parapsilosis ATCC 7330 resulted in the formation of the (R)-enantiomers in high enantiomeric excesses (up to >99%) and isolated yields (up to 79%). (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2008.07.012

文献信息

• Enantioselective oxidation of secondary alcohols by <i>Candida parapsilosis</i> ATCC 7330
  作者：Thakkellapati Sivakumari、Radhakrishnan Preetha、Anju Chadha

  DOI：10.1039/c3ra46206d

  日期：——

  Optically pure (R) allylic alcohols and (R) 4-phenylbutan-2-ols were prepared via oxidative kinetic resolution using whole cells of Candida papapsilosis ATCC 7330.

  通过使用Candida papapsilosis ATCC 7330的整细胞，通过氧化动力分辨法制备了光学纯的(R)烯丙醇和(R) 4-苯基丁-2-醇。
• Enantioselective reduction of α,β-enones using an oxazaborolidine catalyst generated in situ from a chiral lactam alcohol
  作者：Yasuhiro Kawanami、Yudai Mikami、Kazuya Kiguchi、Yuki Harauchi、Ryo C. Yanagita

  DOI：10.1016/j.tetasy.2011.10.018

  日期：2011.11

  The oxazaborolidine catalyst prepared in situ from the chiral lactam alcohol 3 and 4-iodophenoxyborane was found to catalyze the enantioselective reduction of α,β-enones at −40 °C with a high level of enantioselectivity of up to 90% ee.

  发现由手性内酰胺醇3和4-碘苯氧基硼烷原位制备的恶唑硼烷催化剂在-40℃下以高达90％ee的高对映选择性催化α，β-烯酮的对映选择性还原。
• Biocatalytic Enantioselective Oxidation of <i>Sec</i> ‐Allylic Alcohols with Flavin‐Dependent Oxidases
  作者：Somayyeh Gandomkar、Etta Jost、Doris Loidolt、Alexander Swoboda、Mathias Pickl、Wael Elaily、Bastian Daniel、Marco W. Fraaije、Peter Macheroux、Wolfgang Kroutil

  DOI：10.1002/adsc.201900921

  日期：2019.11.19

  oxidation of allylic alcohols is challenging to perform in a chemo- as well as stereo-selective fashion at the expense of molecular oxygen using conventional chemical protocols. Here, we report the identification of a library of flavin-dependent oxidases including variants of the berberine bridge enzyme (BBE) analogue from Arabidopsis thaliana (AtBBE15) and the 5-(hydroxymethyl)furfural oxidase (HMFO) and

  使用常规化学方案，以化学和立体选择性方式进行烯丙基醇的氧化具有挑战性，而以分子氧为代价。在这里，我们报告的黄素依赖性氧化酶文库的鉴定，包括拟南芥（AtBBE15）和5-（羟甲基）糠醛氧化酶（HMFO）的小variant碱桥酶（BBE）类似物的变体及其变体（V465T，V465S ，V465T / W466H和V367R / W466F）用于仲烯丙基醇的对映选择性氧化。众所周知，伯醇和苄醇以及某些糖会被黄素依赖性氧化酶转化，但除单篇报道外，尚未对仲烯丙基醇进行研究。所研究的模型底物以动力学分辨率对映体被氧化，其E值高达> 200。例如HMFO V465S / T将（E）-oct-3-en-2-ol（1a）和（E）-4-苯基丁-3-en-2-ol的（S）-对映异构体氧化为E> 200得到的剩余（R）醇在50％的转化率下ee> 99％。如果介质工程需要通过添加助溶剂（例如二甲亚砜）来降低对映选择性。
• A Chiral Electrophilic Selenium Reagent To Promote the Kinetic Resolution of Racemic Allylic Alcohols
  作者：Marcello Tiecco、Lorenzo Testaferri、Claudio Santi、Cristina Tomassini、Rosaria Bonini、Francesca Marini、Luana Bagnoli、Andrea Temperini

  DOI：10.1021/ol048001+

  日期：2004.12.1

  [reaction: see text] The first example of a kinetic resolution process promoted by electrophilic selenium reagents is reported. Racemic allylic alcohols react with half equivalents of a selenenylating agent in methanol leading to the regiospecific formation of the corresponding addition products with a very high level of facial selectivity (from 95:5 to 98:2 dr). The unreacted alcohols can be recovered

  [反应：见正文]报告了由亲电子硒试剂促进的动力学拆分过程的第一个例子。外消旋烯丙醇与甲醇中半当量的硒烯化剂反应，导致具有非常高的面部选择性（从95：5至98：2 dr）的相应加成产物区域特异性形成。未反应的醇可以光学富集的形式（从90％到94％ee）回收。
• Aminocyclopentadienyl Ruthenium Complexes as Racemization Catalysts for Dynamic Kinetic Resolution of Secondary Alcohols at Ambient Temperature
  作者：Jun Ho Choi、Yoon Kyung Choi、Yu Hwan Kim、Eun Sil Park、Eun Jung Kim、Mahn-Joo Kim、Jaiwook Park

  DOI：10.1021/jo0355799

  日期：2004.3.1

  tests in the racemization of (S)-4-phenyl-2-butanol showed that 7 is the most active catalyst, although the difference decreased in the DKR. Complex 4 was used in the DKR of various alcohols; at room temperature, not only simple alcohols but also functionalized ones such as allylic alcohols, alkynyl alcohols, diols, hydroxyl esters, and chlorohydrins were successfully transformed to chiral acetates. In

  Aminocyclopentadienyl钌复合物，其可以用作常温消旋催化剂与在动态动力学拆分仲醇的（DKR），脂肪酶是从环戊-2,4- dienimines合成的Ru 3（CO）12，和CHCl 3： [2,3,4,5-PH 4（η 5 -C 4 CNHR）]的Ru（CO）2 Cl（上4：R =我-Pr; 5：R = ñ -Pr; 6：R =吨-Bu ），[2,5-ME 2 -3,4--PH 2（η 5 -C 4 CNHR）]的Ru（CO）2 Cl（上7：R = i -Pr; 8：R = PH），和[2,3,4,5-PH 4（η 5 -C 4 CNHAr）]的Ru（CO）2 Cl（上9：Ar为p -NO 2 ç 6 ħ 4 ; 10： Ar ＝p- ClC 6 H 4；11：Ar ＝ Ph；12：Ar ＝p- OMeC 6 H 4；13：Ar ＝p- NMe 2 C 6 H 4）。外消旋