1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol
• 英文别名: (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]-2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol；R,R-bpzmmH；(1R)-1-[(1R,5S)-6,6-dimethyl-2-bicyclo[3.1.1]hept-2-enyl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol
• 化学式: C₂₁H₃₀N₄O
• 分子量: 354.495
• InChiKey: FCLKFMMGBYZRKF-YTQUADARSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  55.9
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-{(1R)-6,6-dimethyl-bicyclo[3.1.1]-2-hepten-2-yl}-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol 、 三乙基铝 以 甲苯 为溶剂， 反应 2.0h， 以93%的产率得到
  参考文献：
  名称：

  杂铝酸铝配合物催化合成环状碳酸酯

  摘要：

  已经制备了新的基于蝎铝酸铝的配合物，并将其用于由环氧化物和二氧化碳合成环状碳酸酯。双金属铝（杂蝎子酸盐）络合物9 – 14的合成产率很高。的单晶X射线结构12和13确认的不对称κ 2中的双核分子处置-NO-μ-O布置。研究了这些双金属铝络合物作为在铵盐存在下由环氧化物和二氧化碳合成环状碳酸酯的催化剂。在最佳反应条件下，络合物9与四丁基溴化铵联用可作为一种非常有效的催化剂体系，用于将单取代和内部环氧化物均转化为相应的环状碳酸酯，从而显示出较宽的底物范围。配合物9和四丁基溴化铵是第二种最有效的铝基催化剂体系，用于内部环氧化物与二氧化碳的反应。进行了动力学研究，结果表明反应在络合物9和四丁基溴化铵浓度下是一级反应。基于动力学研究，提出了催化循环。

  DOI：

  10.1002/chem.201500790

文献信息

• On the Search for NNO-Donor Enantiopure Scorpionate Ligands and Their Coordination to Group 4 Metals
  作者：Antonio Otero、Juan Fernández-Baeza、Juan Tejeda、Agustín Lara-Sánchez、Margarita Sánchez-Molina、Sonia Franco、Isabel López-Solera、Ana M. Rodríguez、Luis F. Sánchez-Barba、Sonia Morante-Zarcero、Andrés Garcés

  DOI：10.1021/ic900352e

  日期：2009.6.15

  2-bis(3,5-dimethylpyrazol-1-yl)ethanol} was obtained with an excellent diastereomeric excess (>99% de) in a one-pot process utilizing the aldehyde (1R)-(−)-myrtenal as a chiral substrate to control the stereochemistry of the newly created asymmetric center. These new chiral heteroscorpionate ligands reacted with [MX4] (M = Ti, Zr; X = NMe2, OiPr, OEt, OtBu) in a 1:1 molar ratio in toluene to give,

  以锂衍生物[Li（bpzb）（THF）]的形式制备新的手性双（吡唑-1-基）甲烷基NNO供体蝎形酸酯配体[ 1；bpzb = 1,1-双（3,5-二甲基吡唑-1-基）-3,3-二甲基-2-丁氧基]和[Li（bpzte）（THF）] [ 2 ; bpzte = 2,2-双（3,5-二甲基吡唑-1-基）-1-对甲苯氧基]或醇配体（bpzbH）（3）和（bpzteH）（4）已进行1,2与三甲基乙醛或对甲苯甲醛的加成反应。醇配体3外消旋混合物的分离已通过三个合成步骤实现了对映体纯NNO醇-蝎酸酯配体：（i）将1，2-将适当的锂衍生物加成至三甲基乙醛，（ii）酯化和分离非对映异构体5，（iii）皂化。随后，对映体纯蝎子配体（R，R）-bpzmmH 6 ; R，R -bpzmmH =（1 R）-1-[（1 R）-6,6-二甲基双环[3.1.1] 2-庚-2-基] -2,2-双（3,5-二甲基吡唑-使用醛（1
• Stereoselective ROP of <i>rac</i>-Lactide Mediated by Enantiopure NNO-Scorpionate Zinc Initiators
  作者：Manuel Honrado、Antonio Otero、Juan Fernández-Baeza、Luis F. Sánchez-Barba、Andrés Garcés、Agustı́n Lara-Sánchez、Ana M. Rodrı́guez

  DOI：10.1021/om500207x

  日期：2014.4.14

  2 and 5 were also unambiguously established. Alkyl- and aryloxide/thioaryloxide-containing enantiopure zinc complexes 3–6 and 9 can act as single-component living initiators for the ring-opening polymerization of lactides, affording materials with low molecular weights under mild conditions in only a few hours. Interestingly, microstructural analysis of poly(rac-lactide) by 1H NMR spectroscopy revealed

  对映体纯NNO-蝎形配体（R，R）-bpzmmH与[ZnR 2 ]（R = Me，Et，CH 2 SiMe 3）的摩尔比为1：2的反应得到双核三烷基[Zn（R ）（κ 2 -NNμ-O）的Zn（R）2 ]（R =我（1），等（2），CH 2森达3（3））。双金属三烷基组成的反应1 - 3与芳族醇和含有芳醚/ arylthioxide配体硫醇，得到双核锌配合物[（ZNR）2（κN：κN-μ-O）（μ-EAR）]（Ar为2,6--C 6 ħ3我2 ; E = O，R = Me（4），Et（5），CH 2 SiMe 3（6）；E ＝ S，R ＝ Me（7），Et（8），CH 2 SiMe 3（9））通过醇解或硫醇解反应。通过光谱法确定不同化合物的结构，此外，还明确地确定了2和5的X射线晶体结构。含烷基和芳氧基/硫代芳氧基的对映纯锌配合物3 – 6和9丙交酯可以用作丙交酯开环聚合的单组分活性引发剂
• Chiral <i>N</i>,<i>N</i>,<i>O</i>-Scorpionate Zinc Alkyls as Effective and Stereoselective Initiators for the Living ROP of Lactides
  作者：Antonio Otero、Juan Fernández-Baeza、Luis F. Sánchez-Barba、Juan Tejeda、Manuel Honrado、Andrés Garcés、Agustín Lara-Sánchez、Ana M. Rodríguez

  DOI：10.1021/om300146n

  日期：2012.6.11

  pseudo-first-order dependence on monomer and catalyst concentration. 1H NMR and MALDI-TOF mass spectra confirmed that the initiation occurs through nucleophilic attack of alkyl on the lactide monomer. Microstructural analysis of poly(rac-lactide) by 1H NMR spectroscopy revealed that the myrtenal substituent on the alkoxide fragment has a moderate influence on the degree of stereoselectivity, producing at

  手性和对映体纯的基于双（吡唑-1-基）甲烷的NNO供体蝎形配体，呈醇化合物形式（bpzbeH）[bpzbe = 1,1-双（3,5-二甲基吡唑-1-基） -3,3-二甲基-2-丁氧基]，（bpzteH）[bpzte = 2,2-双（3,5-二甲基吡唑-1-基）-1-对甲苯甲酸]和（R，R）-bpzmmH （R，R）-bpzmm =（1 R）-1-[（1 R）-6,6-二甲基双环[3.1.1] -2-庚-2-基] -2,2-双（3， 5-二甲基吡唑-1-基乙氧基}已被用于获得新的NNO-蝎子酸烷基锌络合物。bpzbeH，bpzteH（外消旋混合物）或（R，R）-bpzmmH（对映体）与[ZnMe 2]在一个1：在甲苯中，得到单核细胞和单烷基锌络合物[锌（Me）的摩尔比为2:1（κ 3 -NNO）]（1 - 3），分别。但是，当使用[ZnEt 2 ]，[Zn t Bu 2 ]或[Zn（CH 2
• Versatile organoaluminium catalysts based on heteroscorpionate ligands for the preparation of polyesters
  作者：J. Martínez、M. Martínez de Sarasa Buchaca、F. de la Cruz-Martínez、C. Alonso-Moreno、L. F. Sánchez-Barba、J. Fernandez-Baeza、A. M. Rodríguez、A. Rodríguez-Diéguez、J. A. Castro-Osma、A. Otero、A. Lara-Sánchez

  DOI：10.1039/c8dt01553h

  日期：——

  A series of alkyl aluminium complexes based on heteroscorpionate ligands were designed as catalysts for the ring-opening polymerisation of cyclic esters and ring-opening copolymerisation of epoxides and anhydrides. Treatment of AlX3 (X = Me, Et) with ligands bpzbeH [bpzbe = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide], bpzteH [bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-para-tolylethoxide]

  设计了一系列基于杂蝎子配体的烷基铝配合物，作为环酯的开环聚合和环氧化物和酸酐的开环共聚的催化剂。用配体bpzbe H [bpzbe = 1,1-双（3,5-二甲基吡唑-1-基）-3,3-二甲基-2-丁醇]，bpzte H [bpzte ]处理AlX 3（X = Me，Et）＝ 2，2-双（3，5-二甲基吡唑-1-基）-1-对甲苯甲酸]，和（R，R）-bpzmm H [（R，R）-bpzmm ＝（1R）-1- （1 R）-6,6-二甲基-双环[3.1.1] -2-庚-2-基} -2,2-双（3,5-二甲基吡唑-1-基）乙醇]在0°C下放置2小时单核二烷基铝配合物[阿尔梅2 κ 2 -bpzbe}]（1），[ALET 2 κ 2 -bpzbe}]（2），[阿尔梅2 κ 2 - （[R ，- [R）-bpzmm}]（3）和[ALET 2 κ 2 - （[R ，- [R）-bpzmm}]（4），和双核二烷基配合物[阿尔梅2
• Heteroscorpionate Rare-Earth Catalysts for the Hydroalkoxylation/Cyclization of Alkynyl Alcohols
  作者：Javier Martínez、Antonio Otero、Agustín Lara-Sánchez、José Antonio Castro-Osma、Juan Fernández-Baeza、Luis F. Sánchez-Barba、Ana M. Rodríguez

  DOI：10.1021/acs.organomet.6b00203

  日期：2016.6.13

  The chiral, enantiopure bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the alcohol compounds bpzbeH (bpzbe = 1,1-bis(3,5-dimethylpyr az ol- 1-y1)-3,3- dim e thy1-2-but oxide), bpzteH (bpzte = 2,2-bis(3,5-dimethylpyrazol-l-y1)-1-p-tolylethoxide), and (R,R)-bpzmmH ((R,R)-bpzmm = (1R)-1-(1R)-6,6dimethylbicydo [3.1.1]-2-hepten-2-yl}-2,2-bis (3,5-climethylpyrazol-1-yl)ethoxide) have been used to obtain new NNOheteroscorpionate yttrium and lutetium complexes. The reactions of bpzbeH, bpzteH (racemic mixtures), and (R,R)bpzmmH (enantiopure compound) with [MN(SiH.Me-2)(2)}(3)(thf)(2)] (M = Y, Lu) in a 1:1 molar ratio mononuclear bis(silylamide) complexes [MN(SiHMe2)(2)}(2)(x(3)-NNO)(thf)] (M = Y, Lu; 1-6), respectively. "When the reaction was carried out with a 2:1 molar ratio (ligand to metal precursor) or with excess ligand, homoleptic complexes of the type [Y(kappa 3NNO)(2)(x-O-NN)] (kappa(3)-NNO = x-O-NN = bpzbe (7), bpzte (8)) were obtained. Compounds 1 and 3 were used as convenient starting materials for the synthesis of the aryloxide and alkoxide yttrium compounds [Y(OR)(2)(x(3)-bpzbe)] (OR = 0-2,6-Me2C6H3 (9), O-CH2(2-CH C)C6H4 (10)) and [Y(OR)(2)(kappa(3)-bpzte)] (OR = O-2,6-Me2O6H3 (11),O-CH2(2-CH=C)C6H4 (12)). The structures of the complexes were determined by spectroscopic methods, and the X-ray crystal structures of 1, 2, and 7 were also established. Complexes 1-6 are efficient catalysts for the intramolecular hydroalkoxylation of alkynyl alcohols and give TOF values up to 19.4 at 90 degrees C for (2-ethynylphenyl)methanol (13) by using the single enantiopure complex 5 as catalyst, producing exclusively the exo-methylene products. The activation parameters Delta H-double dagger = 19.93(0.2) kcal/mol, Delta S-double dagger = 28.75(0.2) eu, and E-a = 18.61(0.2) kcal/mol are consistent with observations for other catalyst-mediated insertive hydroelementation processes.