(R)-3,3-dimethylbutane-1,2-diol | 31612-63-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-3,3-dimethylbutane-1,2-diol
• 英文别名: (R)-2-(tert-butyl)-1,2-ethanediol；(2R)-3,3-dimethyl-1,2-butanediol；(R)-3,3-dimethyl-butane-1,2-diol；(-)-3,3-dimethylbutane-1,2-diol；(R)-3,3-dimethyl-1,2-butanediol；(R)-3,3-dimethyl-butane-1,2-diol；(2R)-3,3-dimethylbutane-1,2-diol
• CAS: 31612-63-2
• 化学式: C₆H₁₄O₂
• 分子量: 118.176
• InChiKey: YVHAOWGRHCPODY-YFKPBYRVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  8
• 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：

  (R)-3,3-dimethylbutane-1,2-diol 在 吡啶 、 sodium hydroxide 、 氨 作用下， 以 甲醇 为溶剂， 反应 200.5h， 生成 (2R)-1-[bis[(2R)-2-hydroxy-3,3-dimethylbutyl]amino]-3,3-dimethylbutan-2-ol
  参考文献：
  名称：

  Early Transition Metal Alkoxide Complexes Bearing Homochiral Trialkanolamine Ligands

  摘要：

  Enantiomerically pure trialkanolamines of the formula N(CH(2)CHROH)(3), where R = methyl (3a), cyclohexyl (3b), tert-butyl (3c), or phenyl (3d), are readily synthesized by the reaction of ammonia with 3 equiv of an enantiopure epoxide. Trialkanolamines 3a-d replace n-propanol in tri-n-propyl vanadate to afford corresponding complexes 4a-d of the formula LV=O, where L is the deprotonated trialkanolamine. Similarly, (S,S,S)-triisopropanolamine 3a reacts with Ti((OPr)-Pr-i)(4) to produce monomeric LTi((OPr)-Pr-i), 7a, which upon treatment with acetyl chloride gives the chloro complex LTiCl, 7b. The later group 5 ethoxides react with 3a to produce LM(OEt)(2) (M = Nb, Ta). Partial hydrolysis of the Nb and Ta derivatives produces tetrameric mu-oxo-bridged structures which retain the trialkanolamine ligands. In all complexes the transition metal resides in a highly asymmetric environment, suggesting that this class of complexes may find use in the field of asymmetric catalysis. The X-ray crystal structures of complexes 4c and 7b are reported.

  DOI：

  10.1021/ja00093a011
• 作为产物：
  描述：

  3,3-二甲基-1-丁烯 在 potassium osmate(VI) 、 dihydroquinidine 0-O-(9'-phenanthryl) ether 、 potassium carbonate 、 potassium hexacyanoferrate(III) 、 叔丁醇 作用下， 以 水 为溶剂， 生成 (R)-3,3-dimethylbutane-1,2-diol
  参考文献：
  名称：

  Early Transition Metal Alkoxide Complexes Bearing Homochiral Trialkanolamine Ligands

  摘要：

  Enantiomerically pure trialkanolamines of the formula N(CH(2)CHROH)(3), where R = methyl (3a), cyclohexyl (3b), tert-butyl (3c), or phenyl (3d), are readily synthesized by the reaction of ammonia with 3 equiv of an enantiopure epoxide. Trialkanolamines 3a-d replace n-propanol in tri-n-propyl vanadate to afford corresponding complexes 4a-d of the formula LV=O, where L is the deprotonated trialkanolamine. Similarly, (S,S,S)-triisopropanolamine 3a reacts with Ti((OPr)-Pr-i)(4) to produce monomeric LTi((OPr)-Pr-i), 7a, which upon treatment with acetyl chloride gives the chloro complex LTiCl, 7b. The later group 5 ethoxides react with 3a to produce LM(OEt)(2) (M = Nb, Ta). Partial hydrolysis of the Nb and Ta derivatives produces tetrameric mu-oxo-bridged structures which retain the trialkanolamine ligands. In all complexes the transition metal resides in a highly asymmetric environment, suggesting that this class of complexes may find use in the field of asymmetric catalysis. The X-ray crystal structures of complexes 4c and 7b are reported.

  DOI：

  10.1021/ja00093a011

文献信息

• Highly Selective Hydrolytic Kinetic Resolution of Terminal Epoxides Catalyzed by Chiral (salen)Co^III Complexes. Practical Synthesis of Enantioenriched Terminal Epoxides and 1,2-Diols
  作者：Scott E. Schaus、Bridget D. Brandes、Jay F. Larrow、Makoto Tokunaga、Karl B. Hansen、Alexandra E. Gould、Michael E. Furrow、Eric N. Jacobsen

  DOI：10.1021/ja016737l

  日期：2002.2.1

  The hydrolytic kinetic resolution (HKR) of terminal epoxides catalyzed by chiral (salen)Co(III) complex 1 x OAc affords both recovered unreacted epoxide and 1,2-diol product in highly enantioenriched form. As such, the HKR provides general access to useful, highly enantioenriched chiral building blocks that are otherwise difficult to access, from inexpensive racemic materials. The reaction has several

  由手性 (salen)Co(III) 配合物 1 x OAc 催化的末端环氧化物的水解动力学拆分 (HKR) 提供了回收的未反应环氧化物和高度对映体富集形式的 1,2-二醇产物。因此，HKR 提供了从廉价的外消旋材料中获得有用的、高度对映体富集的手性结构单元的通用途径，而这些结构单元在其他方面难以获得。从实用的角度来看，该反应具有几个吸引人的特点，包括使用 H(2)O 作为反应物和低负载 (0.2-2.0 mol%) 的可回收、市售催化剂。此外，HKR 显示出非凡的范围，因为可以将各种空间和电子变化的环氧化物分解为 > 或 = 99% ee。相应的 1,2-二醇是使用 0.45 当量的 H(2)O 在良好到高对映体过量中产生的。提供了用于分离高度对映体富集的环氧化物和二醇以及催化剂回收和再循环的有用和通用的协议。HKR 反应的选择性因子 (k(rel)) 通过测量约 ee 的产物 ee 来确定。20%
• Scope and Mechanism of the Pt-Catalyzed Enantioselective Diboration of Monosubstituted Alkenes
  作者：John R. Coombs、Fredrik Haeffner、Laura T. Kliman、James P. Morken

  DOI：10.1021/ja4041016

  日期：2013.7.31

  The Pt-catalyzed enantioselective diboration of terminal alkenes can be accomplished in an enantioselective fashion in the presence of chiral phosphonite ligands. Optimal procedures and the substrate scope of this transformation are fully investigated. Reaction progress kinetic analysis and kinetic isotope effects suggest that the stereodefining step in the catalytic cycle is olefin migratory insertion

  Pt 催化的末端烯烃的对映选择性二硼化可以在手性亚膦酸酯配体存在下以对映选择性方式完成。对这种转化的最佳程序和底物范围进行了充分研究。反应进程动力学分析和动力学同位素效应表明催化循环中的立体定义步骤是烯烃迁移插入 Pt-B 键。密度泛函理论分析与其他实验数据相结合，表明插入反应将铂定位在基板的内部碳上。该反应的立体化学模型得到了改进，该模型既符合这些特征又符合 Pt-配体复合物的晶体结构。
• Hydrolytic Kinetic Resolution of Epoxides Catalyzed by Chromium(III)-endo,endo-2,5-diaminonorbornane-salen [Cr(III)-DIANANE-salen] Complexes. Improved Activity, Low Catalyst Loading
  作者：Albrecht Berkessel、Erkan Ertürk

  DOI：10.1002/adsc.200606181

  日期：2006.12

  The hydrolytic kinetic resolution (HKR) of terminal epoxides, using chiral chromium(III)-salen catalysts based on DIANANE (endo,endo-2,5-diaminonorbornane), was studied. A broad substrate scope was found for the chromium(III)-DIANANE catalysts, and very low loadings (down to 0.05 mol %) were needed to achieve high enantiomeric purities of both the remaining epoxides and the product diols (up to >99 %

  研究了基于DIANANE（内，内--2,5-二氨基降冰片烷）的手性铬（III）-salen催化剂对末端环氧化物的水解动力学拆分（HKR）。发现铬（III）-二亚胺催化剂具有广泛的底物范围，并且需要极低的负载量（低至0.05 mol％）以实现剩余的环氧化物和产物二醇的高对映体纯度（最高> 99％ee））。除单取代的环氧化物外，在电子调谐的铬（III）-二亚胺的存在下，可以以不对称的方式用水将2-甲基-2-正戊基环氧乙烷（2,2-二取代的环氧化物的一个例子）开环。复杂的。
• Asymmetric reactions based on 1,3-oxathianes3̄
  作者：Kwang-Youn Ko、William J. Frazee、Ernest L. Eliel

  DOI：10.1016/s0040-4020(01)82419-4

  日期：1984.1

  prepared1 chiral 2-acyl-l,3-oxathianes derived from (+)-pulegone with various metal hydride combinations proceeds stereoselectively, with diastereomer excess (d.e.) of as much as 97% in the case of reduction of phenyl ketones with lithium tri-sec.butylborohydride. Lesser selectivity (maximum 82% d.e.) is achieved with primary or tertiary alkyl ketones: the predominant diastereomer is readily purified

  减少先前准备的1（+）-普勒高酮与各种金属氢化物的混合物衍生的手性2-酰基-1,3-氧杂蒽基化合物进行立体选择性反应，在用三仲锂还原苯基酮的情况下，非对映体过量（de）高达97％丁基硼氢化物。伯或叔烷基酮的选择性较低（最大为82％de）：主要的非对映异构体易于通过色谱法纯化。在这些情况下，主要产品是克拉姆的螯合法则所预测的。产物比率用氢化二异丁基丁基铝反转，并且在仲锂还原仲烷基酮中也是如此。丁基硼氢化物，立体选择性低。用N-氯代琥珀酰亚胺-硝酸银将2-羟烷基-1,3-氧杂蒽基裂解为α-羟醛，并将醛还原为乙二醇RCHOHCH 2OH与硼氢化钠很少或没有外消旋作用。酯类，RCHOHCO 2 CH 3，是通过在裂解之前对2-羟基烷基-1,3-氧杂蒽基进行O-苄基化，裂解后用亚氯酸钠氧化，酯化和脱苄基而获得的高对映体纯度。一种通过将苯甲醛转化为2-苯基-1,3-二氧戊环并随后对所得的2-苯基-4-烷基-1
• A New Practical Method for the Osmium-Catalyzed Dihydroxylation of Olefins­ using Bleach as the Terminal Oxidant
  作者：Matthias Beller、Gerald M. Mehltretter、Santosh Bhor、Markus Klawonn、Christian Döbler、Uta Sundermeier、Markus Eckert、Hans-Christian Militzer

  DOI：10.1055/s-2003-36826

  日期：——

  A general procedure for the osmium-catalyzed dihydroxylation of various olefins using bleach as oxidant is reported for the first time. Aromatic and aliphatic olefins yield the corresponding cis-1,2-diols in the presence of dihydroquinine or dihydroquinidine derivatives (Sharpless ligands) with good to excellent chemo- and enantioselectivities under optimized pH conditions. In the presence of a small

  首次报道了使用漂白剂作为氧化剂对各种烯烃进行锇催化二羟基化的一般程序。芳香族和脂肪族烯烃在二氢奎宁或二氢奎尼丁衍生物（Sharpless 配体）存在下产生相应的 cis-1,2-二醇，在优化的 pH 条件下具有良好至优异的化学和对映选择性。在少量过量的漂白剂作为再氧化剂的情况下，即使在 0°C 也会发生快速二羟基化。在最佳反应条件下，可以将末端脂肪族和芳香族烯烃以及内烯烃二羟基化。氧化剂的低价和漂白剂的简单处理使这种二羟基化变体对进一步的应用具有吸引力。