(±)-3,3-dimethylpentane-2,4-diol | 24892-50-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (±)-3,3-dimethylpentane-2,4-diol
• 英文别名: (2RS,4RS)-3,3-dimethylpentane-2,4-diol；d,l-3,3-Dimethyl-2,4-pentandiol；dl-3,3-dimethyl-2,4-pentanediol；rac-3,3-Dimethyl-2,4-pentandiol；racem. 3,3-dimethyl-pentane-2,4-diol；meso-threo-3,3-Dimethyl-pentan-2,4-diol；(2S,4S)-3,3-dimethylpentane-2,4-diol
• CAS: 24892-50-0；25140-13-0；25140-14-1；55671-97-1
• 化学式: C₇H₁₆O₂
• 分子量: 132.203
• InChiKey: FVSGQDYLPCUSNF-WDSKDSINSA-N

物化性质

• 沸点：
  80-82 °C(Press: 2 Torr)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (±)-3,3-dimethylpentane-2,4-diol 在 四氯化钛 、 对甲苯磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 12.5h， 生成 rel-(4(R,S),1'R,3'S)-4-(3'-hydroxy-1',2',2'-trimethylbutoxy)-1-decene
  参考文献：
  名称：

  On the stereoselectivity opening of achiral dioxane acetals

  摘要：

  The stereoselectivity of allylation of achiral dioxane acetals cis- and trans-3 and cis- and trans-5 was found to be highly dependent on the nature of the allylmetal reagent, Lewis acid, and stoichiometry. Using TiCl2(O-i-Pr)2 as the Lewis acid in conjunction with allyltrimethylsilane and allyltri-n-butylstannane the selectivity of opening ranged from 1/1 to 18.6/1. In reactions with allyltrimethylsilane, the lack of selectivity for both the cis and trans series (1-2.4/1) was shown to arise from rapid equilibration of ion pairs. Control experiments revealed that the acetals underwent opening faster than isomerization. The reactions with allyltri-n-butylstannane were more selective and dependent on reagent stoichiometry. Moreover, the sense of asymmetric induction for the cis and trans series was opposite. Control experiments again established that isomerization of the acetals occurs slower than reaction with the stannane. These experiments unambiguously rule out the possibility that the opening proceeds via equilibrating ion pairs. The meso dioxane acetal cis-9 reacted with significantly reduced selectivity compared to the 2,4,6-trisubstituted analogue cis-7. On the other hand, the chiral acetal (+/-)-13 reacted much more selectively than the 2,4,6-trisubstituted analogue (+/-)-11. These reactions illustrate the sensitivity of stereochemical outcome to structural and experimental variables and demonstrate the ability to intercept reactive ion pairs under conditions of kinetic control.

  DOI：

  10.1021/jo00022a043
• 作为产物：
  描述：

  4-Hydroxy-3,3-dimethyl-2-pentanon 在 palladium on activated charcoal 锂硼氢 、 氢气 、 sodium hydride 、 pyridinium tetrafluoroborate 、 对甲苯磺酸 、 丙酮 作用下， 以 甲醇 、 乙醚 、 苯 为溶剂， 反应 27.25h， 生成 (±)-3,3-dimethylpentane-2,4-diol
  参考文献：
  名称：

  Maier, Guenther; Seipp, Ulrich; Kalinowski, Hans-Otto, Chemische Berichte, 1994, vol. 127, # 8, p. 1427 - 1436

  摘要：

  DOI：

文献信息

• Brønsted Acid Catalyzed Asymmetric Reduction of Ketones and Acyl Silanes Using Chiral <i>anti</i>-Pentane-2,4-diol
  作者：Jun-ichi Matsuo、Yu Hattori、Hiroyuki Ishibashi

  DOI：10.1021/ol1006532

  日期：2010.5.21

  Ketones and acyl silanes were reduced to the corresponding alcohols by a simple procedure employing anti-1,3-diol and a catalytic amount (5 mol %) of 2,4-dinitrobenzenesulfonic acid in benzene at reflux. Asymmetric induction reached up to >99% ee when a chiral pentane-2,4-diol of 97% ee was used.

  通过使用抗-1，3-二醇和催化量（5mol％）的2，4-二硝基苯磺酸在苯中的回流简单方法，将酮和酰基硅烷还原为相应的醇。当使用97％ee的手性戊烷-2,4-二醇时，不对称诱导达到> 99％ee。
• Asymmetric reduction of aliphatic ketones and acyl silanes using chiral anti-pentane-2,4-diol and a catalytic amount of 2,4-dinitrobenzenesulfonic acid
  作者：Jun-ichi Matsuo、Yu Hattori、Mio Hashizume、Hiroyuki Ishibashi

  DOI：10.1016/j.tet.2010.06.012

  日期：2010.8

  Aliphatic ketones were reduced to the corresponding secondary alcohols by using anti-1,3-diol and a catalytic amount of 2,4-dinitrobenzenesulfonic acid (DNBSA) in benzene at reflux. Addition of 1-octanethiol in that media improved the efficiency of the reduction. Asymmetric reduction of aliphatic ketones was performed by using chiral anti-pentane-2,4-diol, and highly asymmetric induction (up to >99%

  通过使用抗-1,3-二醇和催化量的苯中的2,4-二硝基苯磺酸（DNBSA），在回流下将脂肪族酮还原为相应的仲醇。在该介质中加入1-辛硫醇可提高还原效率。通过使用手性抗戊烷-2,4-二醇进行脂族酮的不对称还原，并且在叔烷基酮的还原中观察到高度不对称的诱导作用（最高> 99％ee）。在不存在辛硫醇的情况下，使用手性抗戊烷-2,4-二醇和DNBSA进行的酰基硅烷的不对称还原有效地进行，并以高收率和高ee收率获得了相应的α-甲硅烷基醇。
• Chemistry of 1,3-Glycol Derivatives. IV. Mechanism of the Solvolyses of 2,4-Pentanediol Derivatives and the Reactions of the Proposed Intermediate Acetoxonium Ions with Carbanions and Hydride
  作者：Osamu Itoh、Naoki Iwakoshi、Toshihide Saitoh、Hiroaki Katano、Yoshiki Fujisawa、Yoshinori Hasegawa、Toshio Sugita、Katsuhiko Ichikawa

  DOI：10.1246/bcsj.55.177

  日期：1982.1

  stereochemical studies of the solvolyses of various kinds of 2,4-pentanediol derivatives, including 2-acetoxy-4-tosylates, cyclic orthoformates and orthoacetates, have been done and the previously proposed mechanism has been partially revised. The reactions of the proposed intermediate acetoxonium ions with carbanions and with a hydride ion have also been studied.

  已经对各种 2,4-戊二醇衍生物（包括 2-乙酰氧基-4-甲苯磺酸酯、环状原甲酸酯和原乙酸酯）的溶剂分解进行了区域和立体化学研究，并且对先前提出的机制进行了部分修改。还研究了所提出的中间体乙酰氧离子与碳负离子和氢阴离子的反应。
• Asymmetric Hydrogenation of<i>tert</i>-Alkyl Ketones: DMSO Effect in Unification of Stereoisomeric Ruthenium Complexes
  作者：Tomoya Yamamura、Hiroshi Nakatsuka、Shinji Tanaka、Masato Kitamura

  DOI：10.1002/anie.201304408

  日期：2013.8.26

  Face off: The ruthenium complexes of a new axially chiral PNN ligand (L) are highly efficient in the presence of dimethylsulfoxide (DMSO) for hydrogenation of both functionalized and unfunctionalized tert‐alkyl ketones. DMSO is thought to narrow down the many possible complex stereoisomers into a single facial L/Ru complex, thus enhancing the reactivity, selectivity, and productivity.

  面临的挑战：新型的轴向手性PNN配体（L）的钌络合物在二甲基亚砜（DMSO）的存在下对官能化和未官能化叔烷基酮的加氢都非常有效。DMSO被认为可以将许多可能的复杂立体异构体缩小为单个面部L / Ru复杂物，从而提高了反应性，选择性和生产率。
• Cazaux,L.; Maroni,P., Bulletin de la Societe Chimique de France, 1972, p. 780 - 785
  作者：Cazaux,L.、Maroni,P.

  DOI：——

  日期：——