(S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol

• 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: (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol
• 英文别名: 2,4-ditert-butyl-6-[[(2S)-2-[hydroxy(diphenyl)methyl]pyrrolidin-1-yl]methyl]phenol
• 化学式: C₃₂H₄₁NO₂
• 分子量: 471.683
• InChiKey: WMWDNPFWLHTXGM-NDEPHWFRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  35
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  43.7
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol 、 氯化二乙基铝 以 甲苯 为溶剂， 反应 2.0h， 以92%的产率得到(S)-{O^O}AlCl
  参考文献：
  名称：

  由手性酚基-脯氨醇二阴离子配体支持的铝、镓和铟配合物

  摘要：

  摘要 由脯氨醇衍生的对映异构纯苯酚-烷氧基 {OˆO}2− 双阴离子三齿配体支持的三烯金属的同系配合物 (S)-{OˆO}MCH2SiMe3 (M=Al, 3; Ga, 5; In, 6)，连同它们的氯衍生物，已被制备和表征。铝-烷基物质 (S)-{O^O}AlMe 和 3 形成四配位配合物，四面体几何形状略有扭曲，而路易斯酸性五配位 (S)-{O^O}GaCl·THF 中的几何形状是扭曲的三角双锥。这些烷基配合物不会与质子源完全反应，如果有的话。铟 (III) 化合物 6，例如，即使在 70°C 下数小时后仍对 iPrOH 或 BnOH 呈惰性，在 95°C 下催化受控、在作为链转移剂的过量 BnOH 存在下，外消旋丙交酯（高达 1000 当量）的永生开环聚合。它提供具有可预测分子量的无规立构单分散聚交酯。

  DOI：

  10.1515/mgmc-2016-0036
• 作为产物：
  描述：

  2,4-二叔丁基苯酚 在 三乙胺 、 magnesium chloride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 8.5h， 生成 (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol
  参考文献：
  名称：

  Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ with Phenoxy-Functionalized Chiral Prolinols

  摘要：

  A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee.

  DOI：

  10.1021/acs.orglett.5b00833
• 作为试剂：
  描述：

  2-(4-methoxybenzylidene)-1-tetralone 在 叔丁基过氧化氢 、 [(Me₃Si)₂N]₃Yb(μ-Cl)Li(THF)₃ 、 (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以99%的产率得到(2S,3'R)-3'-(4-methoxyphenyl)spiro[3,4-dihydronaphthalene-2,2'-oxirane]-1-one
  参考文献：
  名称：

  Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ with Phenoxy-Functionalized Chiral Prolinols

  摘要：

  A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee.

  DOI：

  10.1021/acs.orglett.5b00833

文献信息

• Asymmetric Epoxidation of Unsaturated Ketones Catalyzed by Heterobimetallic Rare Earth–Lithium Complexes Bearing Phenoxy-Functionalized Chiral Diphenylprolinolate Ligand
  作者：Qinqin Qian、Yufang Tan、Bei Zhao、Tao Feng、Qi Shen、Yingming Yao

  DOI：10.1021/ol5020398

  日期：2014.9.5

  Four novel heterobimetallic complexes [REL2][(THF)3Li]2(μ-Cl)} stabilized by chiral phenoxy-functionalized prolinolate (RE = Yb (1), Y (2), Sm (3), Nd (4), H2L = (S)-2,4-di-tert-butyl-6-[[2-(hydroxydiphenylmethyl)pyrrolidin-1-yl]methyl]phenol have been synthesized and characterized. These readily available complexes are highly active in catalyzing the epoxidation of α,β-unsaturated ketones, while

  四种新型双核配合物[REL 2 ] [（THF）3李] 2（μ-Cl）的}通过手性苯氧基官能化prolinolate稳定（RE =镱（1），Y（2），SM（3），钕（4），H 2 L =（小号）-2,4-二-叔已经合成并表征了丁基-6-[[[2-（羟基二苯基甲基）吡咯烷-1-基]甲基]苯酚。这些容易获得的络合物在催化α，β-不饱和酮的环氧化中具有高活性，而对映选择性根据稀土中心的离子半径而变化。在10 mol％的1存在下，使用TBHP作为氧化剂，在0°C于80→99％ee下，将一系列查尔酮衍生物转化为手性环氧化物。
• Asymmetric Michael addition of malonates to unsaturated ketones catalyzed by rare earth metal complexes bearing phenoxy functionalized chiral diphenylprolinolate ligands
  作者：Qinqin Qian、Wenguo Zhu、Chengrong Lu、Bei Zhao、Yingming Yao

  DOI：10.1016/j.tetasy.2016.07.014

  日期：2016.10

  A simple, efficient catalytic asymmetric Michael addition of malonates to unsaturated ketones has been successfully developed. This process was promoted by rare earth metal complexes 1-4 bearing a chiral phenoxy functionalized prolinol ligand at room temperature [(LRE)-R-1((LH)-H-1) (H2L1 = (S)-2,4-di-tert-butyl-6-(2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol, RE = Yb 1, Y 2, Sc 3 and (LSc)-Sc-2((LH)-H-2) 4 (H2L2 = (S)-2,4-di-dimethylbenzy1-6-(2-(hydroxydiphenylmethyl)-pyrrolidin-1-yl)methyl)phenol)]. Complex 3 was the best catalyst in the transformation and the products were obtained in,up to 99% yield and with 90% ee. In addition, the molecular structures of the catalysts were well characterized, including X-ray determination of complex 3. (C) 2016 Elsevier Ltd. All rights reserved.
• Highly Enantioselective Epoxidation of α,β-Unsaturated Ketones Catalyzed by Rare-Earth Amides [(Me₃Si)₂N]₃RE(μ-Cl)Li(THF)₃ with Phenoxy-Functionalized Chiral Prolinols
  作者：Chao Zeng、Dan Yuan、Bei Zhao、Yingming Yao

  DOI：10.1021/acs.orglett.5b00833

  日期：2015.5.1

  A simple and efficient catalytic enantioselective epoxidation of alpha,beta-unsaturated ketones has been successfully developed, which was catalyzed by rare-earth metal amides [(Me3Si)(2)N](3)RE(mu-Cl)Li(THF)(3) (RE = Yb (1), La (2), Sm (3), Y (4), Lu (5)) in the presence of phenoxy-functionalized chiral prolinols at room temperature using tert-butylhydroperoxide (TBHP) as the oxidant. The combination of an Yb-based amide 1 and a chiral proligand (S)-2,4-di-tert-butyl-6-((2-(hydroxydiphenylmethyl)pyrrolidin-1-yl)methyl)phenol) performed very well, and both the yields and the enantiomeric excess of the chiral epoxides reached up to 99% and 99% ee.
• Aluminium, gallium and indium complexes supported by a chiral phenolato-prolinolato dianionic ligand
  作者：Nicolas Maudoux、Eric Tan、Yuya Hu、Thierry Roisnel、Vincent Dorcet、Jean-François Carpentier、Yann Sarazin

  DOI：10.1515/mgmc-2016-0036

  日期：2016.1.1

  Abstract Congeneric complexes (S)-OˆO}MCH2SiMe3 (M=Al, 3; Ga, 5; In, 6) of the triel metals supported by an enantiomerically pure phenolato-alkoxo OˆO}2− dianionic tridentate ligand derived from prolinol, along with their chloro derivatives, have been prepared and characterised. The aluminium-alkyl species (S)-OˆO}AlMe and 3 form four-coordinate complexes with slightly distorted tetrahedral geometries

  摘要 由脯氨醇衍生的对映异构纯苯酚-烷氧基 OˆO}2− 双阴离子三齿配体支持的三烯金属的同系配合物 (S)-OˆO}MCH2SiMe3 (M=Al, 3; Ga, 5; In, 6)，连同它们的氯衍生物，已被制备和表征。铝-烷基物质 (S)-O^O}AlMe 和 3 形成四配位配合物，四面体几何形状略有扭曲，而路易斯酸性五配位 (S)-O^O}GaCl·THF 中的几何形状是扭曲的三角双锥。这些烷基配合物不会与质子源完全反应，如果有的话。铟 (III) 化合物 6，例如，即使在 70°C 下数小时后仍对 iPrOH 或 BnOH 呈惰性，在 95°C 下催化受控、在作为链转移剂的过量 BnOH 存在下，外消旋丙交酯（高达 1000 当量）的永生开环聚合。它提供具有可预测分子量的无规立构单分散聚交酯。