(R,R)-α,α'-di-tert-butyl-2,6-pyridinedimethanol | 156129-02-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: (R,R)-α,α'-di-tert-butyl-2,6-pyridinedimethanol
• 英文别名: (S,S)-(-)-2,6-bis(1'-hydroxy-2',2'-dimethylpropyl)pyridine；1,1'-(pyridine-2,6-diyl)bis(2,2-dimethylpropan-1-ol)；(1S)-1-[6-[(1S)-1-hydroxy-2,2-dimethylpropyl]pyridin-2-yl]-2,2-dimethylpropan-1-ol
• CAS: 156129-02-1
• 化学式: C₁₅H₂₅NO₂
• 分子量: 251.369
• InChiKey: YHNMSFIVSJLRGC-CHWSQXEVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.24
• 重原子数：
  18.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  53.35
• 氢给体数：
  2.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (R,R)-α,α'-di-tert-butyl-2,6-pyridinedimethanol 在 chromium(VI) oxide 、 硫酸 、 二异丙胺 、 二乙醇胺 、 (-)-diisopinocamphenylborane chloride 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 49.5h， 生成 (R,R)-(+)-2-(1'-hydroxy-2',2'-dimethylpropyl)-6-(1''-methoxymethyloxy-2'',2''-dimethylpropyl)pyridine
  参考文献：
  名称：

  Catalysed asymmetric reaction of aldehydes with dialkylzinc in the presence of chiral pyridyl alcohols as ligands

  摘要：

  The synthesis of homochiral pyridyl alcohols (1,2,3a-c) and a catalytic asymmetric addition of dialkylzinc to various aldehydes using 1-3 as ligands are described. Although the reaction of benzaldehyde with Et2Zn in the presence of (S)-1 and (R,R)-2 gave (S)- and (R)-1-phenyl-1-propanol, respectively, in moderate enantiomeric excess (e.e.), tridentate ligands (3a-c) accelerated the reaction to produce the corresponding alcohols in high e.e. Particularly, (S)-3b was found to be the most efficient catalyst, for which asymmetric reactions of various aldehydes with dialkylzinc gave the corresponding alcohols in good to high e.es. (up to 95% e.e.).

  DOI：

  10.1016/s0957-4166(00)86213-8
• 作为产物：
  描述：

  meso-2,6-bis(1'-hydroxy-2',2'-dimethylpropyl)pyridine 在 chromium(VI) oxide 、 硫酸 、 二乙醇胺 、 (+)-二异松蒎基氯硼烷 作用下， 以 丙酮 为溶剂， 反应 1.5h， 生成 (R,R)-α,α'-di-tert-butyl-2,6-pyridinedimethanol
  参考文献：
  名称：

  Catalysed asymmetric reaction of aldehydes with dialkylzinc in the presence of chiral pyridyl alcohols as ligands

  摘要：

  The synthesis of homochiral pyridyl alcohols (1,2,3a-c) and a catalytic asymmetric addition of dialkylzinc to various aldehydes using 1-3 as ligands are described. Although the reaction of benzaldehyde with Et2Zn in the presence of (S)-1 and (R,R)-2 gave (S)- and (R)-1-phenyl-1-propanol, respectively, in moderate enantiomeric excess (e.e.), tridentate ligands (3a-c) accelerated the reaction to produce the corresponding alcohols in high e.e. Particularly, (S)-3b was found to be the most efficient catalyst, for which asymmetric reactions of various aldehydes with dialkylzinc gave the corresponding alcohols in good to high e.es. (up to 95% e.e.).

  DOI：

  10.1016/s0957-4166(00)86213-8

文献信息

• A Highly Active Manganese Catalyst for Enantioselective Ketone and Ester Hydrogenation
  作者：Magnus B. Widegren、Gavin J. Harkness、Alexandra M. Z. Slawin、David B. Cordes、Matthew L. Clarke

  DOI：10.1002/anie.201702406

  日期：2017.5.15

  A new hydrogenation catalyst based on a manganese complex of a chiral P,N,N ligand has been found to be especially active for the hydrogenation of esters down to 0.1 mol % catalyst loading, and gives up to 97 % ee in the hydrogenation of pro‐chiral deactivated ketones at 30–50 °C.

  已发现一种新的基于手性P，N，N配体的锰配合物的加氢催化剂对于酯加氢至低至0.1摩尔％的催化剂负载特别有效，并且在加氢脱氢反应中可产生高达97％ee在30–50°C下手性失活的酮。
• Chiral Synthesis via Organoboranes. 46. An Efficient Preparation of Chiral Pyridino- and Thiopheno-18-crown-6 Ligands from Enantiomerically Pure <i>C</i>₂-Symmetric Pyridine- and Thiophenediols¹
  作者：Guang-Ming Chen、Herbert C. Brown、P. Veeraraghavan Ramachandran

  DOI：10.1021/jo980899r

  日期：1999.2.1

  high de and ee. Asymmetric allylboration of 2,6-pyridinedicarboxaldehyde and 2,5-thiophenedicarboxaldehyde provides the corresponding bis-homoallylic alcohols in very high de and ee. These optically pure diols were converted to the disodium or dipotassium salts and treated with tetra(ethylene glycol) ditosylate to obtain the corresponding chiral pyridino and thiopheno-18-crown-6 ligands. However, the

  与B-chlorodiisopinocampheylborane不对称还原2,6-二酰基吡啶提供非常高的de和ee中相应的C（2）对称二醇。2，6-吡啶二甲醛和2，5-噻吩二甲醛的不对称烯丙基硼化以非常高的de和ee提供了相应的双均烯丙基醇。将这些旋光纯的二醇转化为二钠盐或二钾盐，并用四（乙二醇）二甲苯磺酸酯处理以获得相应的手性吡啶基和噻吩-18-冠-6配体。但是，全氟烷基二醇不能提供大环。
• Asymmetric epoxidation models: An alkyl hydroperoxide dependent change in mehanism
  作者：Joel M Hawkins、K.Barry Sharpless

  DOI：10.1016/s0040-4039(00)96219-1

  日期：1987.1
• New Pyridino-18-crown-6 Ligands Containing Two Methyl, Two <i>tert</i>-Butyl, or Two Allyl Substituents on Chiral Positions Next to the Pyridine Ring
  作者：Yoichi Habata、Jerald S. Bradshaw、J. Jolene Young、Steven L. Castle、Peter Huszthy、Tongjin Pyo、Milton L. Lee、Reed M. Izatt

  DOI：10.1021/jo960474+

  日期：1996.1.1

  Chiral 2,16-diallyl-, 2,16-dimethyl-, and 2,16-di-tert-butylpyridino-18-crown-6 Ligands have been. prepared by treating the appropriate chiral alpha,alpha'-disubstituted pyridinedimethanol with tetraethylene glycol ditosylate in the presence of base. In these reactions, chiral 2:2 dimers (dipyridino-36-crown-12 derivatives) were also obtained. The log K values for the interaction of these chiral ligands with the enantiomers of (alpha-phenylethyl)ammonium perchlorate (PhEt) and (alpha-(1-naphthyl)ethyl)-ammonium perchlorate (NapEt) were measured using an H-1 NMR titration method in a CDCl3/CD3OD (1/1) solvent mixture. The log K values indicate that these chiral pyridino-18-crown-6 ligands have high complexing abilities and some enantiomeric recognition for the chiral organic ammonium perchlorates. The H-1 NMR titration experiments also show that the phenyl ring of the guest PhEt is approximately parallel to the pyridine ring in the chiral diallyl- and dimethyl-substituted Ligand complexes with chiral PhEt and the phenyl ring is perpendicular to the pyridine ring in the chiral di-tert-butyl-substituted ligand complex with PhEt. These results were supported by MM2 calculations.