((4R,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene) bis-(2,2-dimethylpropanoate) | 163964-60-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ((4R,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene) bis-(2,2-dimethylpropanoate)
• CAS: 163964-60-1
• 化学式: C₁₇H₃₀O₆
• 分子量: 330.422
• InChiKey: OJOQMZKXSOESGX-TXEJJXNPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  23.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  ((4R,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene) bis-(2,2-dimethylpropanoate) 在 氢氧化钾 、 SAM II_. lipase 作用下， 以 甲醇 、 水 为溶剂， 反应 51.0h， 生成 (+)-1-O-acetyl-2,3-O-isopropylidene-L-erythritol
  参考文献：
  名称：

  Pottie, M.; Lathauwer, G. De; Vandewalle, M., Bulletin des Societes Chimiques Belges, 1994, vol. 103, # 5-6, p. 285 - 294

  摘要：

  DOI：
• 作为产物：
  描述：

  三甲基乙酰氯 在 吡啶 、 对甲苯磺酸 作用下， 生成 ((4R,5S)-2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene) bis-(2,2-dimethylpropanoate)
  参考文献：
  名称：

  Investigation of Diastereoselective Acyclic α-Alkoxydithioacetal Substitutions Involving Thiacarbenium Intermediates

  摘要：

  Reported herein is an experimental and theoretical study that elucidates why silylated nucleobase additions to acyclic alpha-alkoxythiacarbenium intermediates proceed with high 1,2-syn stereocontrol (anti-Felkin-Anh), which is opposite to what would be expected with corresponding activated aldehydes. The acyclic thioaminals formed undergo intramolecular cyclizations to provide nucleoside analogues with anticancer and antiviral properties. The factors influencing the selectivity of the substitution reaction have been examined thoroughly. Halothioether species initially form, ionize in the presence (low dielectric media) or absence (higher dielectric media) of the nucleophile, and react through S(N)2-like transition structures (TS A and D), where the a-alkoxy group is gauche to the thioether moiety. An important, and perhaps counterintuitive, observation in this work was that calculations done in the gas phase or low dielectric media (toluene) are essential to locate the product- and rate-determining transition structures (C-N bond formation) that allow the most reasonable prediction of selectivity and isotope effects for more polar solvents (THF, MeCN). The triangle triangle G +/- (G(TSA)-(TSD)) obtained in silico are consistent with the preferential formation of 1,2-syn product and with the trends of stereocontrol displayed by 2,3-anti and 2,3-syn alpha,beta-bis-alkoxydithioacetals.

  DOI：

  10.1021/jo502181a

文献信息

• Desymmetrization of <i>meso</i>-1,2-Diols by a Chiral <i>N</i>,<i>N</i>-4-Dimethylaminopyridine Derivative Containing a 1,1′-Binaphthyl Unit: Importance of the Hydroxy Groups
  作者：Hiroki Mandai、Hiroshi Yasuhara、Kazuki Fujii、Yukihito Shimomura、Koichi Mitsudo、Seiji Suga

  DOI：10.1021/acs.joc.7b00992

  日期：2017.7.7

  We developed an acylative desymmetrization of meso-1,2-diols using a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1h with tert-alcohol substituents. The reaction proceeds with a wide range of acyclic meso-1,2-diols and six-membered-ring meso-1,2-diols to provide a monoacylate selectively with a high enantiomeric ratio (er). Only 0.1 mol % of the catalyst facilitated the reaction within

  我们开发了使用基于叔萘基的N，N -4-二甲基氨基吡啶（DMAP）衍生物1h和叔醇取代基的内消旋-1,2-二醇的酰基化不对称化反应。反应以各种无环的内消旋-1，2-二醇和六元环的内消旋-1，2-二醇进行，以选择性地提供具有高对映体比率（er）的单酰化物。仅0.1mol％的催化剂在短的反应时间（3h）内促进了反应，以中等至良好的产率提供了对映体富集的单酰化产物。几个对照实验表明，催化剂1h的叔醇单元 在实现高催化活性，单酰化的化学选择性和对映选择性方面起着重要作用。