(2R,4S)-3,3-dimethylpentane-2,4-diol | 25140-14-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R,4S)-3,3-dimethylpentane-2,4-diol
• 英文别名: meso-3,3-dimethyl-2,4-pentanediol；meso-3,3-Dimethyl-2,4-pentandiol；meso-3,3-dimethyl-pentane-2,4-diol；meso-3,3-Dimethyl-pentan-2,4-diol；3,3-Dimethyl-pentan-2,4-diol
• CAS: 25140-14-1
• 化学式: C₇H₁₆O₂
• 分子量: 132.203
• InChiKey: FVSGQDYLPCUSNF-OLQVQODUSA-N

物化性质

• 熔点：
  60-70 °C(mixture of isomers)
• 沸点：
  118 °C(Press: 16 Torr)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.77
• 重原子数：
  9.0
• 可旋转键数：
  2.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (2R,4S)-3,3-dimethylpentane-2,4-diol 在 四氯化钛 、 对甲苯磺酸 作用下， 以 二氯甲烷 、 苯 为溶剂， 反应 3.5h， 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 27.75h， 生成 (2R,4S)-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

• 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。
• Cazaux,L.; Maroni,P., Bulletin de la Societe Chimique de France, 1972, p. 780 - 785
  作者：Cazaux,L.、Maroni,P.

  DOI：——

  日期：——
• Asymmetric Hydrosilylation of Symmetrical Diketones Catalyzed by a Rhodium Complex with Trans-Chelating Chiral Diphosphine EtTRAP
  作者：R Kuwano

  DOI：10.1016/00404-0399(50)0981h-

  日期：1995.7.17
• Diastereoselectivity in the Reduction of Acyclic Carbonyl Compounds with Diisopropoxytitanium(III) Tetrahydroborate
  作者：K. S. Ravikumar、Surajit Sinha、S. Chandrasekaran

  DOI：10.1021/jo9902906

  日期：1999.8.1

  Diisopropoxytitanium(III) tetrahydroborate, ((PrO)-Pr-i)(2)TiBH4, formed in situ in dichloromethane from diisopropoxytitanium dichloride and benzyltriethylammonium tetrahydroborate (1:2) reduces alpha-hydroxyketones/1,2-diketones and beta-hydroxyketones/1,3-diketones to the corresponding diols with high stereoselectivity. In the case of alpha-hydroxyketones and 1,2-diketones, the anti isomer is the major product while reduction of beta-hydroxyketones and 1,3-diketones leads to the syn isomer as the major product.
• Diastereoselection in the LiA1H4 reduction of severely hindered β-diketones examples of -curtin-hammett preequilibrium conditions
  作者：Marcial Moreno-Mañas、Nicanor Galvez、Maria E. Lloris、Jorge Marquet、Antonio C. Siani

  DOI：10.1016/s0040-4020(01)88498-2

  日期：1992.1

  LiAlH4 Reduction of alpha-adamantyl (and tert-butyl)-beta-diketones occur under anti-Curtin-Hammett preequilibrium conditions, each preferred conformer leading to a different stereoisomeric diol, whereas reduction of 3-adamantyl-3-methyl (and ethyl)pentane-2,4-dione occurs with high diastereoselectivity to afford only the (2R, 3r, 4S) meso diol.