trans-2,2,4,5-tetramethyl-1,3-dioxolane | 73346-75-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-2,2,4,5-tetramethyl-1,3-dioxolane
• 英文别名: (4R,5R)-2,2,4,5-Tetramethyl-1,3-dioxolane
• CAS: 73346-75-5
• 化学式: C₇H₁₄O₂
• 分子量: 130.187
• InChiKey: IWHKRVPYJLOGAW-PHDIDXHHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  9
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-2,2,4,5-tetramethyl-1,3-dioxolane 在 2,3,5-三甲基吡啶 、 tri-tert-butoxysilanethiol 作用下， 以 various solvent(s) 为溶剂， 反应 2.5h， 生成 (R,S)-2,2,4,5-tetramethyl-1,3-dioxolane
  参考文献：
  名称：

  Selective radical-chain epimerisation at CH centres α to oxygen under conditions of polarity-reversal catalysis

  摘要：

  Polarity-reversal catalysis by tri-tert-butoxysilanethiol has been applied to promote radical-chain epimerisation selectively at carbon centres of the type (RRC)-R-1-C-2*(H)OR. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00704-2
• 作为产物：
  描述：

  (R,S)-2,2,4,5-tetramethyl-1,3-dioxolane 在 2,3,5-三甲基吡啶 、 tri-tert-butoxysilanethiol 作用下， 以 various solvent(s) 为溶剂， 反应 2.5h， 生成 trans-2,2,4,5-tetramethyl-1,3-dioxolane
  参考文献：
  名称：

  Selective radical-chain epimerisation at CH centres α to oxygen under conditions of polarity-reversal catalysis

  摘要：

  Polarity-reversal catalysis by tri-tert-butoxysilanethiol has been applied to promote radical-chain epimerisation selectively at carbon centres of the type (RRC)-R-1-C-2*(H)OR. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)00704-2

文献信息

• Analytical enantiomer separation of aliphatic diols as boronates and acetals by complexation gas chromatography
  作者：V. Schurig、D. Wistuba

  DOI：10.1016/s0040-4039(01)91399-1

  日期：1984.1

  Cyclic boronates and acetals of mono- and dialkylsubstituted 1,2-, 2,3- 1,3- & 1,4- diols have been quantitatively separated into enantiomers by complexation gas chromatography utilizing optically active metal chelates. An efficient, precise & sensitive method for determining enantiomeric purities for volatile glycols is thus available.

  单和二烷基取代的1,2-，2,3-，1,3-和1,4-二醇的环状硼酸酯和缩醛已通过利用光学活性金属螯合物的络合气相色谱法定量分离为对映体。因此，可以使用一种有效，精确和灵敏的方法来测定挥发性二醇的对映体纯度。
• Selective oxidation of O-isopropylidene derivatives of diols to 2-hydroxy ketones employing dioxiranes
  作者：Ruggero Curci、Lucia D'Accolti、Anna Dinoi、Caterina Fusco、Angela Rosa

  DOI：10.1016/0040-4039(95)02087-x

  日期：1996.1

  transformed into homochiral 2-hydroxy ketones in high optical yield, and with preservation of configuration at the C∗OH chiral center proximal to that undergoing oxidation to carbonyl. The diacetonide of 1,4-Diphenylbutan-1,2:3,4-tetraol could be selectively converted into 1,4-diphenyl-1-oxo-2-hydroxy 3,4-acetonide, with removal of just one acetonide moiety.

  使用二甲基二环氧乙烷（1a）或甲基（三氟甲基）二环氧乙烷（1b），可以在温和的条件下高产率地将1,2-二醇的O-异亚丙基衍生物直接转化为相应的2-羟基酮。旋光性乙炔化物以高光学收率转化为同手性2-羟基酮，并在靠近C ＝ OH的手性中心处保留构型，该构型接近于氧化为羰基的手性中心。可以仅除去一个丙酮化物部分，将1，4-二苯基丁烷-1，2：3，4-四元醇的二丙酮化物选择性地转化为1，4-二苯基-1-氧代-2-羟基3，4-丙酮化物。
• Selective radical-chain epimerisation at electron-rich chiral tertiary C–H centres using thiols as protic polarity-reversal catalysts
  作者：Hai-Shan Dang、Brian P. Roberts、Derek A. Tocher†

  DOI：10.1039/b103558b

  日期：——

  Radical-chain epimerisation at chiral tertiary CH centres adjacent to ethereal oxygen atoms can be brought about in the presence of thiols, the function of which is to act as protic polarity-reversal catalysts for hydrogen-atom transfer between pairs of nucleophilic α-alkoxyalkyl radicals. The viability of the method is demonstrated by epimerisation of a series of simple molecules that contain two chiral centres and then the procedure is applied to more complex carbohydrate-based systems, where it is possible to convert a readily available diastereoisomer into a rarer one in a straightforward manner. Of necessity, epimerisation always proceeds in the direction of thermodynamic equilibrium and, in general, the results obtained are in accord with the predictions of molecular mechanics calculations using the MMX force-field. When the required isomer is less stable than the starting diastereoisomer, thiol-catalysed epimerisation of a suitable derivative of the parent can provide a means to obtain the desired compound in satisfactory yield, after deprotection of the epimerised derivative. This strategy is demonstrated for the conversion of trans-cyclohexane-1,2-diol into the less stable cis-isomer and for related contra-thermodynamic isomerisation of some carbohydrates, as well as for the conversion of meso-1,2-diphenylethane-1,2-diol into the dl-form. Thiol-catalysed epimerisation at a CH centre adjacent to an ether-oxygen atom is much faster than at a similar centre adjacent to an amido-nitrogen atom, a result that can be understood in terms of the importance of polar effects on the rate of abstraction of hydrogen by electrophilic thiyl radicals.

  硫醇的作用是作为亲核δ-烷氧基烷基自由基对之间氢原子转移的原生极性反转催化剂，可以在邻近乙氧基原子的手性三级 CH 中心实现自由基链表并化。通过对一系列含有两个手性中心的简单分子进行外延二聚化，证明了该方法的可行性，然后将该程序应用于更复杂的基于碳水化合物的体系，在这些体系中，可以通过直接的方式将容易获得的非对映异构体转化为较罕见的非对映异构体。必要时，二聚化总是朝着热力学平衡的方向进行，一般来说，所获得的结果与使用 MMX 力场进行分子力学计算的预测结果一致。当所需异构体的稳定性低于起始非对映异构体时，可采用巯基催化母体的适当衍生物进行外延化反应，在对外延化衍生物进行脱保护处理后，以令人满意的收率获得所需化合物。这种策略在反式-1,2-环己烷二醇转化为稳定性较差的顺式异构体、某些碳水化合物的相关逆热力学异构化以及介-1,2-二苯基乙烷-1,2-二醇转化为 dl-形式时得到了验证。邻近醚氧原子的 CH 中心在硫醇催化下的缩合反应要比邻近酰胺氮原子的类似中心快得多，这一结果可以从极性效应对亲电巯基取氢速率的重要性角度来理解。
• Synthesis of Acetonides from Epoxides Catalyzed by Erbium(III) Triflate
  作者：Antonio Procopio、Renato Dalpozzo、Antonio De Nino、Loredana Maiuolo、Monica Nardi、Beatrice Russo

  DOI：10.1002/adsc.200505096

  日期：2005.8

  Epoxides dissolved in acetone can be converted almost quantitatively in acetonides in the presence of catalytic amounts of erbium(III) triflate. The procedure can be usefully applied to other substrates and can be extended to other ketones.

  在催化量的三氟甲磺酸（（III）存在下，溶于丙酮的环氧化物几乎可以在丙酮化物中进行定量转化。该方法可以有用地应用于其他基质，并且可以扩展至其他酮。
• Synthesis of 1,3-dioxolanes by the addition of ketones to epoxides by using [Cp*Ir(NCMe)3]2+ as catalyst
  作者：Richard D. Adams、Thomas S. Barnard、Kellie Brosius

  DOI：10.1016/s0022-328x(99)00039-x

  日期：1999.6

  2-diethyl-4-vinyl-1,3-dioxolane, 5; 2,2-diethyl-4-phenyl-1,3-dioxolane, 6 were prepared from the appropriate epoxide and carbonyl compounds. An inversion of configuration at the carbon atom at the C–O bond cleavage site of the epoxide was observed to occur in the formation of the dioxolanes: R, S,- 2,2,4,5-tetramethyl-1,3-dioxolane, 7 and a mixture of R,R- and S,S-2,2,4,5-tetramethyl-1,3-dioxolane, 8 obtained

  通过在催化剂[Cp * Ir（NCMe）3 ] 2 +，Cp * C 5 Me 5的存在下将酮添加到环氧化物中，制备了一系列1,3-二氧戊环。反应在22℃下容易进行，收率良好。以下1,3-二氧戊环：2,2,4-三甲基-1,3-二氧戊环，1 ; 2,2-二甲基-4-乙烯基-1,3-二氧戊环，2 ; 2,2-二甲基-4-苯基-1,3-二氧戊环，3 ; 2,2-二乙基-4-甲基-1,3-二氧戊环，4 ; 2,2-二乙基-4-乙烯基-1,3-二氧戊环，5 ; 2,2-二乙基-4-苯基-1,3-二氧戊环6由合适的环氧化物和羰基化合物制备。在二氧戊环的形成中观察到发生环氧化物的C–O键裂解位点处碳原子构型的反转：R，S，-2,2,4,5-四甲基-1,3-二氧戊环，7和R，R-和S，S -2,2,4,5-四甲基-1,3-二氧戊环8的混合物，是从丙酮与R，R，-/ S，S，-的反应获得的丁-2-氧化物和R，S，-丁-2-氧化物。

表征谱图