(+)-3-neomenthylindene | 148180-35-2

• 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: (+)-3-neomenthylindene
• 英文别名: 3-[(1S,2S,5R)-5-methyl-2-propan-2-ylcyclohexyl]-1H-indene
• CAS: 148180-35-2
• 化学式: C₁₉H₂₆
• 分子量: 254.415
• InChiKey: IQCRMKOTLPNUPH-ALKREAHSSA-N

物化性质

• 沸点：
  354.6±17.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  6.1
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (+)-3-neomenthylindene 在 甲基锂 作用下， 以 乙醚 为溶剂， 反应 2.0h， 以82%的产率得到(1-neomenthylindenyl)lithium
  参考文献：
  名称：

  The role of torsional isomers of planarly chiral nonbridged bis(indenyl)metal type complexes in stereoselective propene polymerization

  摘要：

  Reaction of enantiomerically pure (1-neomenthylindenyl)lithium with ZrCl4(THF)2 gave the three diastereomeric bis(1-neomenthylindenyl)zirconium dichloride complexes 4a-A,-B,and -C, in a 93:2:5 ratio. Similarly, a 82:7:11 mixture of the three bis(1-neoisomenthylindenyl)zirconium dichloride diastereoisomers (4b-A,B,C) was obtained from (1-neoisomenthylindenyl)lithium and the zirconium tetrachloride-bis(tetrahydrofuran) adduct. Recrystallization from methylene chloride furnished the (optically active) pure diastereomers 4a-A and 4b-A, respectively. Catalytic hydrogenation (PtO2, 50-60 bar of H-2, CH2Cl2) converted them into the pure (p-S, p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5a-A) and (p-R,p-R)-bis(1-neoisomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5b-A) complexes. All four metallocenes were characterized by X-ray crystal structure analyses. Complex 4a-A crystallizes in space group P2 with cell parameters a = 10.510(1) angstrom, b = 6.975(1) angstrom, c = 12.421(1) angstrom, beta = 108.18(1)degrees, Z = 1, R = 0.037, R(w) = 0.041; 4b-A P2(1), a = 7.559(2) angstrom, b = 9.046(2) angstrom, c = 25.015(3) angstrom, beta = 96.72(1)degrees, Z = 2, R = 0.037, R(w) = 0.040; 5a-A P2(1)2(1)2, a = 15.422(1) angstrom, b = 18.716(1) angstrom, c = 7.118(1) angstrom, Z = 2, R = 0.062, R(w) = 0.074; 5b-A P2(1)2(1)2, a = 10.103(1) angstrom, b = 26.626(5) angstrom, c = 6.762(1) angstrom, Z = 2, R = 0.030, R(w) = 0.037. Complexes 4a-A, 5a-A, and 5b-A exhibit C2-symmetric bent metallocene conformations in the crystal which are characterized as having the bulky terpenyl substituents oriented antiperiplanarly toward the lateral sectors of the bent metallocene wedge (''bis-lateral:anti'' conformation). In contrast, the bis(neoisomenthylindenyl)zirconium dichloride complex 4b-A has only one hydrocarbyl substituent arranged laterally whereas the other is oriented to the open front side of the metallocene backbone (C1-symmetric ''central,lateral:gauche'' conformation). In solution the conformational behavior of these complexes is different. By dynamic temperature-dependent H-1 and C-13 NMR spectroscopy both neoisomenthyl-substituted complexes 4b-A and 5b-A appear as single C2-symmetric species in solution. In contrast, the neomenthyl-substituted complexes 4a-A and 5a-A exhibit equilibrating conformational mixtures. In the case of the (p-S,p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride system (5a-A) it was shown that two conformational isomers are present in a ca. 80:20 ratio. These are C2- (major isomer) and C1-symmetric (minor isomer) and probably correspond to the ''bis-lateral:anti'' and ''central,lateral:gauche'' conformational types, respectively, that were identified by X-ray diffraction in the crystal. These conformational properties seem to determine the outcome of the stereoselective propene polymerization to a considerable extent, which was carried out at homogeneous bent metallocene/methylalumoxane Ziegler-type catalysts derived from the complexes 4 and 5. Both neoisomenthyl-substituted systems produce isotactic high molecular weight polypropylene with purely enantiomorphic site control at low temperature. The isomeric neomenthyl-substituted systems are much less stereoselective.It is assumed that the bis(1-neomenthyltetrahydroindenyl)zirconium catalyst switches back and forth between the C2- and C1-symmetric conformations of the bent metallocene backbone during the catalytic process, thereby probably giving rise to the formation of alternating isotactic and near to atactic sequences along the growing polymer chain.

  DOI：

  10.1021/ja00064a022
• 作为产物：
  描述：

  L-薄荷醇 、 alkaline earth salt of/the/ methylsulfuric acid 在 吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 75.0h， 生成 (+)-3-neomenthylindene
  参考文献：
  名称：

  The role of torsional isomers of planarly chiral nonbridged bis(indenyl)metal type complexes in stereoselective propene polymerization

  摘要：

  Reaction of enantiomerically pure (1-neomenthylindenyl)lithium with ZrCl4(THF)2 gave the three diastereomeric bis(1-neomenthylindenyl)zirconium dichloride complexes 4a-A,-B,and -C, in a 93:2:5 ratio. Similarly, a 82:7:11 mixture of the three bis(1-neoisomenthylindenyl)zirconium dichloride diastereoisomers (4b-A,B,C) was obtained from (1-neoisomenthylindenyl)lithium and the zirconium tetrachloride-bis(tetrahydrofuran) adduct. Recrystallization from methylene chloride furnished the (optically active) pure diastereomers 4a-A and 4b-A, respectively. Catalytic hydrogenation (PtO2, 50-60 bar of H-2, CH2Cl2) converted them into the pure (p-S, p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5a-A) and (p-R,p-R)-bis(1-neoisomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride (5b-A) complexes. All four metallocenes were characterized by X-ray crystal structure analyses. Complex 4a-A crystallizes in space group P2 with cell parameters a = 10.510(1) angstrom, b = 6.975(1) angstrom, c = 12.421(1) angstrom, beta = 108.18(1)degrees, Z = 1, R = 0.037, R(w) = 0.041; 4b-A P2(1), a = 7.559(2) angstrom, b = 9.046(2) angstrom, c = 25.015(3) angstrom, beta = 96.72(1)degrees, Z = 2, R = 0.037, R(w) = 0.040; 5a-A P2(1)2(1)2, a = 15.422(1) angstrom, b = 18.716(1) angstrom, c = 7.118(1) angstrom, Z = 2, R = 0.062, R(w) = 0.074; 5b-A P2(1)2(1)2, a = 10.103(1) angstrom, b = 26.626(5) angstrom, c = 6.762(1) angstrom, Z = 2, R = 0.030, R(w) = 0.037. Complexes 4a-A, 5a-A, and 5b-A exhibit C2-symmetric bent metallocene conformations in the crystal which are characterized as having the bulky terpenyl substituents oriented antiperiplanarly toward the lateral sectors of the bent metallocene wedge (''bis-lateral:anti'' conformation). In contrast, the bis(neoisomenthylindenyl)zirconium dichloride complex 4b-A has only one hydrocarbyl substituent arranged laterally whereas the other is oriented to the open front side of the metallocene backbone (C1-symmetric ''central,lateral:gauche'' conformation). In solution the conformational behavior of these complexes is different. By dynamic temperature-dependent H-1 and C-13 NMR spectroscopy both neoisomenthyl-substituted complexes 4b-A and 5b-A appear as single C2-symmetric species in solution. In contrast, the neomenthyl-substituted complexes 4a-A and 5a-A exhibit equilibrating conformational mixtures. In the case of the (p-S,p-S)-bis(1-neomenthyl-4,5,6,7-tetrahydroindenyl)zirconium dichloride system (5a-A) it was shown that two conformational isomers are present in a ca. 80:20 ratio. These are C2- (major isomer) and C1-symmetric (minor isomer) and probably correspond to the ''bis-lateral:anti'' and ''central,lateral:gauche'' conformational types, respectively, that were identified by X-ray diffraction in the crystal. These conformational properties seem to determine the outcome of the stereoselective propene polymerization to a considerable extent, which was carried out at homogeneous bent metallocene/methylalumoxane Ziegler-type catalysts derived from the complexes 4 and 5. Both neoisomenthyl-substituted systems produce isotactic high molecular weight polypropylene with purely enantiomorphic site control at low temperature. The isomeric neomenthyl-substituted systems are much less stereoselective.It is assumed that the bis(1-neomenthyltetrahydroindenyl)zirconium catalyst switches back and forth between the C2- and C1-symmetric conformations of the bent metallocene backbone during the catalytic process, thereby probably giving rise to the formation of alternating isotactic and near to atactic sequences along the growing polymer chain.

  DOI：

  10.1021/ja00064a022

文献信息

• Catalytic cyclometallation of allylbenzenes by EtAlCl2 and Mg as new route to synthesis of dibenzyl butane lignans
  作者：Lyudmila V. Parfenova、Tatyana V. Berestova、Pavel V. Kovyazin、Aydar R. Yakupov、Ekaterina S. Mesheryakova、Leonard M. Khalilov、Usein M. Dzhemilev

  DOI：10.1016/j.jorganchem.2014.09.033

  日期：2014.12

  with EtAlCl2 (Et2AlCl) and Mg in the presence of Zr and Ti catalysts (Dzhemilev reaction) has been studied. The reaction run with high diastereoselectivity and gives cyclic organoaluminum compounds, which deuterolysis or hydrolysis gave 2R(S), 3R(S)-dibenzyl butanes with yield of 48–69%. The study of catalyst structure effect on the substrate conversion, reaction chemo- and stereoselectivity showed

  在Zr和Ti催化剂存在下用EtAlCl 2（Et 2 AlCl）和Mg对烯丙基苯（Ar = Ph，4-MeO-Ph，3,4-（MeO）2 -Ph）进行环金属化反应（Dzhemilev反应）研究过。该反应以高非对映选择性进行，得到环状有机铝化合物，其经氘解或水解得到2 R（S），3 R（S）-二苄基丁烷，产率为48-69％。对催化剂结构对底物转化率，反应化学和立体选择性的影响的研究表明，在Cp 2 ZrCl 2的情况下获得了最佳结果在测试的复合物中。在反应中新薄荷烯基或新薄荷基四氢茚基锆催化剂的对映选择性不超过20％ee。的反式-在反应中形成的所述metallacycles的代用品的结构已经被证明由水解产物的X射线分析- 2 - [R （小号），3 - [R （小号） -二甲基-1,4-双[（4' ）-甲氧基苯基）甲基]丁烷。所提出的方法可用于从容易获得的烯丙基苯一锅法非对映选择性地合成二苄基丁烷木脂素。
• Synthesis of the C1–C16 fragment of ionomycin using a neutral (η³-allyl)iron complex
  作者：John P. Cooksey、Philip J. Kocienski、Ying-fa Li、Stefan Schunk、Thomas N. Snaddon

  DOI：10.1039/b606262h

  日期：——

  Key steps in the synthesis of the C1-C16 polyketide fragment of ionomycin were the nucleophilic addition of an organocuprate to a neutral (eta3-allyl)iron complex and the construction of a beta-diketone moiety by the Rh-catalysed rearrangement of an alpha-diazo-beta-hydroxyketone.

  合成离子霉素C1-C16聚酮化合物片段的关键步骤是向中性（eta3-烯丙基）铁络合物亲核加成有机铜盐，并通过Rh催化的α-重排重新构建β-二酮部分。重氮-β-羟基酮。
• Asymmetric alkene cycloalumination by AlEt3, catalyzed with neomenthylindenyl zirconium η-complexes
  作者：Lyudmila V. Parfenova、Pavel V. Kovyazin、Tatyana V. Tyumkina、Tatyana V. Berestova、Leonard M. Khalilov、Usein M. Dzhemilev

  DOI：10.1016/j.jorganchem.2012.10.021

  日期：2013.1

  structures, as well as solvent, affect the overall yield and enantiomeric excess of the reaction product - 3-alkylsubstituted aluminacyclopentanes. The reaction of terminal alkenes with AlEt3, catalyzed by complex 1, in hydrocarbon solvents gives predominantly S-enantiomers of cyclic organoaluminum compounds with enantiomeric excess up to 37%. Complex 2 shows smaller stereoinduction effect and provides

  纸张致力于末端烯烃cycloalumination的反应通过ALET研究3（对具有neomenthylindenyl锆络合物催化小号）（对小号） -双[ η 5 - [1 - [（1小号，2小号，5 [R）-2-异丙基-5- methylcycloh-exyl]茚基]二氯化锆（1）或（对小号） - （η 5 -环戊二烯基）[ η 5 - [1 - [（1小号，2小号，5 R）-2-异丙基-5-甲基环己基]茚基]]二氯化锆（2）。结果表明，烯烃和催化剂的结构以及溶剂影响了反应产物3-烷基取代的氧化铝环戊烷的总产率和对映体过量。在烃类溶剂中，末端烯烃与配合物1催化的AlEt 3的反应主要产生环状有机铝化合物的S-对映异构体，其对映体过量最高可达37％。配合物2显示较小的立体诱导作用，并提供具有6–26％ee的氧化铝环戊烷的R对映异构体。 显示了含硒的衍生试剂（R）-2-苯基硒基丙酸对由环状有机铝化合物制得的β-烷基-1
• Syntheses of Chiral Nonracemic Half-Sandwich Cobalt Complexes with Menthyl-Derived Cyclopentadienyl, Indenyl, and Fluorenyl Ligands
  作者：Andrey Gutnov、Hans-Joachim Drexler、Anke Spannenberg、Günther Oehme、Barbara Heller

  DOI：10.1021/om030357m

  日期：2004.3.1

  prepared by the alkylation of fluorenyllithium with (−)-menthyltosylate, and the complex (+)-(pseudo-neomenthylfluorenyl)Co(COD) (6) was synthesized by the metathetic reaction of the corresponding lithium salt with (PPh3)3CoCl and COD, in which an inversion of the cyclohexane ring of the terpene moiety was observed upon complexation. The structures of the compounds 1, 2, 3, 4, 5, and 6 were determined by single-crystal

  制备了几种旋光的（Cp R）Co（L）（L ＝ 1，5-环辛二烯，降冰片二烯）配合物。通过在COD存在下用高反应性“原子”钴直接处理（-）-薄荷基环戊二烯，合成了（-）-（薄荷基Cp）Co（COD）（1）。通过将（-）-去质子化来制备（+）- pR-（1-新薄荷烯基）Co（COD）（2）和（+）- pR-（1-新薄荷烯基）Co（NBD）（3）。 3-新萘与BuLi的反应以及相应的锂盐与三（三苯基膦）钴（I）氯化物的易位反应，然后替换PPh 3分别使用COD或NBD。络合物的非对映选择性高达74.5％de，色谱分离出主要的非对映异构体。从（+）-3-新薄荷烯开始，类似地制备光学纯的配合物（-）- pS-（1-新薄荷烯基）Co（COD）（4），主要非对映异构体的非对映异构体过量为74.4％de。通过将芴基锂与（-）-薄荷基甲苯磺酸酯烷基化来制备（+）-新薄荷基芴5，并通过相应锂的易位反应合成络