2-(4-hydroxy-4-phenylbutyl)-2-methyl-1,3-dioxolane | 58568-17-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 2-(4-hydroxy-4-phenylbutyl)-2-methyl-1,3-dioxolane
• 英文别名: 4-(2-methyl-[1,3]dioxolan-2-yl)-1-phenyl-butan-1-ol；4-(2-Methyl-1,3-dioxolan-2-yl)-1-phenylbutan-1-ol
• CAS: 58568-17-5
• 化学式: C₁₄H₂₀O₃
• 分子量: 236.311
• InChiKey: ZGVDYICZSKMNHM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(4-hydroxy-4-phenylbutyl)-2-methyl-1,3-dioxolane 在 盐酸 作用下， 生成 6-Phenyl-6-chlorhexanon-2
  参考文献：
  名称：

  Kuznetsov,N.V.; Myrsina,R.A., Soviet progress in chemistry, 1975, vol. 41, # 12, p. 60 - 63

  摘要：

  DOI：
• 作为产物：
  描述：

  5-氯-2-戊酮 在 联苯 lithium 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 2-(4-hydroxy-4-phenylbutyl)-2-methyl-1,3-dioxolane
  参考文献：
  名称：

  ROMPgel-supported biphenyl and naphthalene: reagents for lithiation reactions with minimal purification

  摘要：

  The synthesis of ring opening metathesis, polymer (ROMPgel) supported naphthalene and biphenyl reagents was carried out. These reagents were utilized for catalytic lithiation reactions of aryl and alkyl chlorides and for the reductive deprotection of benzyl and allyl ethers. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)02317-6

文献信息

• Polymer supported arene-catalysed lithiation reactions
  作者：Cecilia Gómez、Sonia Ruiz、Miguel Yus

  DOI：10.1016/s0040-4020(99)00330-0

  日期：1999.5

  The reaction of functionalised mono or dichlorinated materials 1a–6a with an excess of lithium and a catalytic amount of a naphthalene (PN) or biphenyl (PB) supported polymer (eassily prepared by radical copolymerisation of 2-vinylnaphthalene or 4-vinylbiphenyl with vinylbenzene and divinylbenzene) in THF either in the presence or not of different electrophiles [Me3SiCl, iPrCHO, PhCHO, Et2CO, (CH2)4CO

  官能化的单或二氯化材料的反应1A-6A与过量锂和萘的催化量（P Ñ）或联苯（P乙支持）聚合物（由2-乙烯基萘或4-乙烯基联苯与自由基共聚eassily制备THF中存在或不存在不同的亲电试剂[Me 3 SiCl，i PrCHO，PhCHO，Et 2 CO，（CH 2）4 CO，（CH 2）5 CO，（c -C 3 H 5））2 CO，i Pr 2用水水解后，在−78或−50°C的温度下，CO，PhCOMe，PhCHnNPh]会产生预期的功能化产物1ca-6ck。聚合物催化剂被定量回收并且可以重复使用几次而没有任何活性损失。
• Reductive Lithiation in the Absence of Aromatic Electron Carriers. A Steric Effect Manifested on the Surface of Lithium Metal Leads to a Difference in Relative Reactivity Depending on Whether the Aromatic Electron Carrier Is Present or Absent
  作者：Nicole Kennedy、Gang Lu、Peng Liu、Theodore Cohen

  DOI：10.1021/acs.joc.5b01136

  日期：2015.9.4

  aromatic radical-anions of lithium or lithium metal in the presence of an aromatic electron-transfer catalyst. Here we present results showing that lithium dispersion can achieve reductive lithiation in the absence of the electron-transfer agent. This procedure is more efficient, and surprisingly, the order of reactivity of substrates is reversed depending on whether the electron-transfer agent is

  制备有机锂化合物的最广泛使用的方法之一是在芳族电子转移催化剂存在下，通过烷基苯基硫醚或通常较不方便的烷基卤化物与锂或锂金属的芳族阴离子进行还原锂化。 。在这里，我们给出的结果表明，在没有电子转移剂的情况下，锂分散体可以实现还原锂化。该过程更有效，并且令人惊讶地，取决于电子转移剂是否存在，底物的反应顺序颠倒了。例如，在存在预先形成的自由基阴离子的情况下，叔丁基丁基苯硫醚的裂解速度明显快于甲基苯基苯硫醚，而在不存在自由基阴离子的情况下，正好相反。密度泛函理论计算表明，锂表面上烷基苯基硫醚中C–S键裂解的放热度取决于烷基的大小，烷基越小，放热度越大。反应性的提高归因于烷基和锂表面之间较小的空间排斥。该方法包括但不限于苯基硫醚，烷基氯，丙烯醛二乙基乙缩醛和异色满的锂分散体还原锂化。
• 2-(3-Lithiopropyl)- and 2-(3-lithiopropyl)-2-methyl-1,3-dioxolane: New masked lithium bishomoenolates in the synthesis of bifunctionalized compounds
  作者：Diego J. Ramón、Miguel Yus

  DOI：10.1016/s0040-4039(00)97465-3

  日期：——

  2-(3-Lithiopropyl)- and 2-(3-lithiopropyl)-2-methyl-1,3-dioxolane (2) are prepaned by lithiation of the corresponding chlorinated precursors with lithium naphthalenide at −78°C. The reaction of these masked bishomoenolates with different electrophiles yields the expected monoprotected functional carbonyl compounds (3–12), which can be easily deprotected under acid conditions.

  通过在-78℃下用萘二甲酸锂对相应的氯化前体进行锂化来预沉积2-（3-Lithiopropyl）-和2-（3-lithiopropyl）-2-甲基-1,3-二氧戊环（2）。这些被掩盖的双歧烯酸酯与不同的亲电试剂的反应产生了预期的单保护的羰基官能化合物（3-12），在酸性条件下可以很容易地对其进行脱保护。
• Fundamental Difference in Reductive Lithiations with Preformed Radical Anions versus Catalytic Aromatic Electron-Transfer Agents:<i>N</i>,<i>N-</i>Dimethylaniline as an Advantageous Catalyst
  作者：Nicole Kennedy、Peng Liu、Theodore Cohen

  DOI：10.1002/anie.201508971

  日期：2016.1.4

  which is constantly reactivated by the catalyst, an unconventional catalyst function. The order of relative reactivity is reversed in the two methods as the dominating factor switches from electronic to steric effects of the alkyl substituent. A catalytic amount of N,N‐dimethylaniline (DMA) and Li ribbon can achieve reductive lithiation. DMA is significantly cheaper than alternative catalysts, and conveniently

  预先形成的芳香族自由基阴离子或锂金属和芳香族电子转移催化剂对苯硫醚或烷基氯的还原锂化反应通常用于制备有机锂。本文揭示的是这两种方法本质上是不同的。在溶液中会发生自由基阴离子的还原，而催化反应发生在锂的表面上，而锂会不断地被催化剂重新活化，这是一种非常规的催化剂功能。相对反应性的顺序在两种方法中是相反的，因为主要因素从烷基取代基的电子效应转换为空间效应。催化量的N，N-二甲基苯胺（DMA）和锂带可以实现还原锂化。DMA比其他催化剂便宜得多，并且方便地，当使用DMA作为催化剂时，Li碳带不需要去除氧化物涂层。
• Masked lithium bishomoenolates: useful intermediates in organic synthesis
  作者：Diego J. Ramon、Miguel Yus

  DOI：10.1021/jo00012a012

  日期：1991.6

  The lithiation of the chloro ketals 9 with lithium naphthalenide at -78-degrees-C led to the corresponding masked lithium bishomoenolates 4, which are stable species under these conditions and react with different electrophilic reagents (H2O, D2O, i-PrCHO, PhCHO, MeCOEt, (activated CH2)4CO, (activated CH2)5CO, (activated CH2)7CO, PhCOMe, c-C3H5COPh, PhCN, HCONMe2, PrCO activated N(CH2)4, PhCO activated N(CH2)4, PhCOCl, EtOCOCl, PhCHNPh, and (PhCH2S)2) to give, after hydrolysis with water, the corresponding bifunctionalized compounds 10a-22a, 10b-22b, and 10c-15c. When alkyl halides were used as electrophiles the reaction failed. In the presence of a catalytic amount of the complex CuBr.Me2S, the same reaction with alpha,beta-unsaturated ketones (methyl vinyl ketone or 2-cyclohexanone) yielded the expected products of a 1,4-addition 25a-c and 26b. The deprotection of the masked carbonyl group was easily done by treatment with 2 N hydrochloric acid in THF, so as examples, compounds 27a-29a, 30b, 31b, 32c, and 33c were isolated. The transformation of hemiacetals of the type 27a into substituted tetrahydropyrans was carried out by means of compounds of the type R3SiNu (Nu = H, allyl, CN) in the presence of BF3, so products 34a-41a, 42b, and 43b were prepared. Finally, the in situ oxidation of the deprotected products of the type 27a-arising from the reaction of bishomoenolate 4a with carbonyl compounds-with Jones reagent (for ketones derivatives) or PCC (for aldehydes derivatives) led to the corresponding delta-lactones 44-57.