(R,R)-α,α'-dimethyl-1,3-benzenedimethanol

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (R,R)-α,α'-dimethyl-1,3-benzenedimethanol
• 英文别名: (1R)-1-[3-[(1R)-1-hydroxyethyl]phenyl]ethanol
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: JXGTYKDVCCARGA-HTQZYQBOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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,R)-α,α'-dimethyl-1,3-benzenedimethanol 、 二甲胺 在 甲基磺酰氯 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 0.33h， 以85%的产率得到S,S-C6H4[CH(Me)NMe2]2-1,3
  参考文献：
  名称：

  含有官能化的C 2对称双氨基芳基'Pincer'配体的手性铂和钯配合物

  摘要：

  描述了对映体（氧官能化的）C 2对称的NCN钳形配体的合成。关键步骤是苄基位置的对称官能化，这是通过对映选择性酮还原和随后的立体选择性取代方案实现的。α-烷基取代基的引入对金属结合的空腔具有显着的影响。例如，对α-乙基官能化的钳位配位体进行锂化反应得到的是混合的（烷基）（芳基）锂聚集体，而不是通常在NCN-锂络合物中观察到的双核双（芳基）锂[Li（NCN）] 2物种。对于（反）-金属化反应，当α-取代基的空间需求增加时，反应进行得明显较慢。在不对称的醛醇缩合和氢转移反应中，已经探究了相应的对映纯钯和钌配合物作为对映选择性催化剂的潜力。两个反应产物的低对映体过量表明，这些催化剂不会引起底物的表面区分，并且手性信息必须位于更靠近金属中心的位置。

  DOI：

  10.1016/s0022-328x(01)00667-2
• 作为产物：
  描述：

  (R,R)-α,α'-dimethyl-1,3-benzenedimethanol diacetate 在 sodium hydroxide 作用下， 以 甲醇 为溶剂， 以90%的产率得到(R,R)-α,α'-dimethyl-1,3-benzenedimethanol
  参考文献：
  名称：

  Separation of remote diol and triol stereoisomers by enzyme-catalyzed esterification in organic media or hydrolysis in aqueous media

  摘要：

  The separation of symmetric, remote, secondary diol stereoisomers by steroselective enzyme-catalyzed acetylation with acetic anhydride in anhydrous, low polarity organic solvents or by stereoselective enzyme-catalyzed hydrolysis of the corresponding peracetate in aqueous media is described. Whether or not an alcohol is acetylated or an acetate is hydrolyzed is determined solely by its own stereochemical arrangement and not by the stereochemistry at any other stereogenic center. Since the enzyme used, Amano P lipoprotein lipase from Pseudomonas species, acetylates secondary alcohol stereogenic centers of the (R)-configuration, an (R,R)-diol is converted to its diacetate, a meso-diol is converted to the monoacetate at its (R)-stereogenic center, and an (S,S)-diol is left unchanged. Similarly, when hydrolysis is used, (R)-stereogenic centers are hydrolyzed so that the (R,R)-stereoisomer is converted to the corresponding diol while the (S,S)-stereoisomer remains a diacetate. The resulting mixture is separated, and the remaining acetates are removed by hydrolysis to give diols and triols of high stereochemical purity. Diols successively separated by esterification include alpha,alpha-dimethyl-1,4-benzenedimethanol, 1, alpha,alpha'-dimethyl-1,3-benzenedimethanol, 4, alpha,alpha'-dimethyl-2,6-pyridinedimethanol, 5, and alpha,alpha-dimethyl-4,4-biphenylenedimethanol, 6. For two cases, alpha,alpha'-dimethyl-2,6-pyridinedimethanol, 5, and alpha,alpha',alpha''-trimethyl-1,3,5-benzenetrimethanol, 7, the separation was achieved using the hydrolysis procedure. The stereochemical purity of each of the separated diol stereoisomers was determined by evaluating the NMR spectrum of its bis-MTPA ester. In most cases, it was possible to establish both the stereochemical purity of the fraction and the amount of each contaminating stereoisomer that was present. The diol products are expected to be of value for preparing optically active polymers and optically active crown ethers.

  DOI：

  10.1021/jo00045a042

文献信息

• One-pot synthesis of chiral alcohols from alkynes by CF₃SO₃H/ruthenium tandem catalysis
  作者：Huan Liu、Sensheng Liu、Haifeng Zhou、Qixing Liu、Chunqin Wang

  DOI：10.1039/c8ra02224k

  日期：——

  A practical one-pot synthesis of chiral alcohols from readily available alkynes via tandem catalysis by the combination of CF3SO3H and a fluorinated chiral diamine Ru(II) complex in aqueous CF3CH2OH is described. Very interestingly, the combination of fluorinated catalysts and solvent exhibits a positive fluorine effect on the reactivity and enantioselectivity. A range of chiral alcohols with wide

  描述了通过在 CF 3 CH 2 OH水溶液中结合 CF 3 SO 3 H 和氟化手性二胺 Ru( II )配合物，从现成的炔烃通过串联催化的实用一锅法合成手性醇。非常有趣的是，氟化催化剂和溶剂的组合对反应性和对映选择性表现出积极的氟效应。在简单温和的条件下，以高收率和优异的立体选择性获得了一系列具有广泛官能团耐受性的手性醇。
• Aminocyclopentadienyl Ruthenium Complexes as Racemization Catalysts for Dynamic Kinetic Resolution of Secondary Alcohols at Ambient Temperature
  作者：Jun Ho Choi、Yoon Kyung Choi、Yu Hwan Kim、Eun Sil Park、Eun Jung Kim、Mahn-Joo Kim、Jaiwook Park

  DOI：10.1021/jo0355799

  日期：2004.3.1

  tests in the racemization of (S)-4-phenyl-2-butanol showed that 7 is the most active catalyst, although the difference decreased in the DKR. Complex 4 was used in the DKR of various alcohols; at room temperature, not only simple alcohols but also functionalized ones such as allylic alcohols, alkynyl alcohols, diols, hydroxyl esters, and chlorohydrins were successfully transformed to chiral acetates. In

  Aminocyclopentadienyl钌复合物，其可以用作常温消旋催化剂与在动态动力学拆分仲醇的（DKR），脂肪酶是从环戊-2,4- dienimines合成的Ru 3（CO）12，和CHCl 3： [2,3,4,5-PH 4（η 5 -C 4 CNHR）]的Ru（CO）2 Cl（上4：R =我-Pr; 5：R = ñ -Pr; 6：R =吨-Bu ），[2,5-ME 2 -3,4--PH 2（η 5 -C 4 CNHR）]的Ru（CO）2 Cl（上7：R = i -Pr; 8：R = PH），和[2,3,4,5-PH 4（η 5 -C 4 CNHAr）]的Ru（CO）2 Cl（上9：Ar为p -NO 2 ç 6 ħ 4 ; 10： Ar ＝p- ClC 6 H 4；11：Ar ＝ Ph；12：Ar ＝p- OMeC 6 H 4；13：Ar ＝p- NMe 2 C 6 H 4）。外消旋
• Dynamic Kinetic Resolution of Secondary Diols via Coupled Ruthenium and Enzyme Catalysis
  作者：B. Anders Persson、Fernando F. Huerta、Jan-E. Bäckvall

  DOI：10.1021/jo990447u

  日期：1999.7.1

  Enzymatic acylation of secondary symmetrical diols (as meso/dl mixtures) in combination with ruthenium-catalyzed isomerization of the diol led to efficient dynamic kinetic resolution. In this way, a meso/dl mixture of the diol was transformed to enantiomerically pure (R,R)-diacetate, making efficient use of all the diol material. For some of the flexible substrates, substantial amounts of meso-diacetates

  二级对称二醇的酶促酰化（作为 meso/dl 混合物）与钌催化的二醇异构化相结合，导致有效的动态动力学拆分。通过这种方式，二醇的内消旋/dl 混合物转化为对映异构纯的 (R,R)-二乙酸酯，从而有效利用所有二醇材料。对于一些柔性基材，大量的内消旋二乙酸盐作为副产物形成。结果表明，内消旋产物的主要部分是通过分子内酰基转移途径形成的。
• An efficient preparation of optically pure C2-symmetric aromatic diols by the asymmetric reduction of diacylaromatic compounds with B-chlorodiisopinocampheylborane
  作者：P.Veeraraghavan Ramachandran、Guang-Ming Chen、Zhi-Hui Lu、Herbert C. Brown

  DOI：10.1016/0040-4039(96)00708-3

  日期：1996.5

  Asymmetric reduction of diacylaromatic compounds with B-chlorodiisopinocampheylborane provides the product diols in excellent diastereomeric and enantiomeric purity.

  用B-氯二异opinocampheylborane不对称还原二酰基芳烃化合物可提供具有出色的非对映异构和对映异构纯度的产物二醇。
• 一种多取代手性(1-羟乙基)苯及其不对称合 成方法
  申请人：三峡大学

  公开号：CN108046995B

  公开（公告）日：2021-06-29

  本发明涉及一种多取代手性(1‑羟乙基)苯，具体结构如II所示，同时本发明公开了该化合物一种“两步一锅法”的合成方法。该方法以廉价易得的多乙炔基取代的苯(I)为原料，经过步骤1)：以含氟的醇和水为溶剂，在三氟甲烷磺酸催化下发生水合反应生成中间体酮；步骤2)：直接在反应体系中加入单磺酰手性二胺与金属钌或铑或铱的配合物为催化剂，并加入碱，充入氢气，不对称氢化反应得到产物II，或者直接在反应体系中加入单磺酰手性二胺与金属钌或铑或铱的配合物为催化剂，甲酸钠或甲酸与三乙胺的混合物为氢源，经不对称转移氢化反应得到产物II。该方法操作简便，原料易得、对映选择性和非对映选择性都很高。