R(+)-2,3-(1,1'-binaphthyl-2,2'-diyldimethylene)cyclopenta-1,3-diene | 136425-32-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: R(+)-2,3-(1,1'-binaphthyl-2,2'-diyldimethylene)cyclopenta-1,3-diene
• 英文别名: 3H-Cyclopenta[6,7]cycloocta[2,1-a:3,4-a']dinaphthalene, 5,7-dihydro-, (R)-；hexacyclo[17.8.0.02,11.03,8.013,17.022,27]heptacosa-1(19),2(11),3,5,7,9,13,16,20,22,24,26-dodecaene
• CAS: 136425-32-6
• 化学式: C₂₇H₂₀
• 分子量: 344.456
• InChiKey: VPUHUEOJFDPPMQ-UHFFFAOYSA-N

物化性质

• 沸点：
  616.4±30.0 °C(Predicted)
• 密度：
  1.23±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7
• 重原子数：
  27
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  五羰基铁 、 R(+)-2,3-(1,1'-binaphthyl-2,2'-diyldimethylene)cyclopenta-1,3-diene 在 norbornene 作用下， 以 甲苯 为溶剂， 以45%的产率得到(R,R)-(+)-bis{(2,3-(1,1'-binaphthyl-2,2'-diyldimethylene)cyclopenta-1,3-dienyl)dicarbonyliron}
  参考文献：
  名称：

  Asymmetric synthesis and metalation of a binaphthylcyclopentadiene, a C2-symmetric chiral cyclopentadiene

  摘要：

  The binaphthylcyclopentadiene 5, abbreviated Binap-Cp, is a C2-symmetric annulated cyclopentadiene possessing axial chirality. This diene is efficiently prepared in four steps via (1) the asymmetric coupling of 1-bromo-2-methylnaphthalene (6) with 1-(bromomagnesio)-2-methylnaphthalene (16) in the presence of catalytic amounts of nickel bromide and the chiral phosphine, (R)-1-[(S)-2-(diphenylphosphino)-ferrocenyl]ethyl methyl ether; (2) bromination of enantiomerically enriched 2,2'-dimethyl-1,1'-binaphthalene (17) with N-bromosuccinimide; (3) bisalkylation of cyclopentadiene to form the spiro-annulated binaphthylcyclopentadiene 15; and (4) sigmatropic rearrangement in toluene at 220-degrees-C to yield the fused diene 5. The enantiomeric purity of 5 was confirmed with the use of a chiral lanthanide H-1 NMR shift reagent. The cyclopentadiene 5 was metalated to form the following complexes: the bis(Binap-Cp)dichlorotitanium 19, the bis(Binap-Cp)dichlorozirconium 22, the (Binap-Cp)dicarbonyliodoiron 26, and the (Binap-Cp)dicarbonylmethyliron 27. All complexes were identified by their spectral and physical data. The structure of the bis(Binap-Cp)dichlorotitanium complex 19 was determined by X-ray crystallography (1:1 racemic complex:hexane crystallized in the C2/c space group, a - 29.611 angstrom, b = 10.902 angstrom, c = 15.868 angstrom, beta = 108.41-degrees, d = 1.101 (calcd, Z = 4) g cm-3). The structure was resolved by direct methods and refined by least squares to R = 4.5% (R(w) = 5.7%). The C2-symmetrical nature of the complex was apparent from the 2-fold axis passing through the titanium.

  DOI：

  10.1021/om00056a012
• 作为产物：
  描述：

  以 甲苯 为溶剂， 反应 30.0h， 以79%的产率得到R(+)-2,3-(1,1'-binaphthyl-2,2'-diyldimethylene)cyclopenta-1,3-diene
  参考文献：
  名称：

  Binaphthylcyclopentadiene: A C2-symmetric annulated cyclopentadienyl ligand with axial chirality

  摘要：

  DOI：

  10.1016/s0040-4039(00)99427-9

文献信息

• A Tunable Class of Chiral Cp Ligands for Enantioselective Rhodium(III)-Catalyzed C–H Allylations of Benzamides
  作者：Baihua Ye、Nicolai Cramer

  DOI：10.1021/ja311956k

  日期：2013.1.16

  The lack of robust and tunable chiral versions of cyclopentadienyl (Cp) ligands hampers progress in the development of catalytic asymmetric versions of a myriad of reactions catalyzed by this ubiquitous ligand. Herein, we describe of a class of chiral Cp ligands with tunable steric parameters. Coordinated to transition metals, the ligand creates a well-defined chiral pocket, able to imprint its chirality onto the metal. The corresponding Rh complexes are shown to be excellent catalysts for enantioselective allylation of N-methoxybenzamides via directed C-H functionalizations at very mild conditions. The obtained enantioselectivities are excellent and demonstrate the viability of chiral Cp complexes as selective transition metal catalysts.
• Enantioselective C–H Bond Addition of Pyridines to Alkenes Catalyzed by Chiral Half-Sandwich Rare-Earth Complexes
  作者：Guoyong Song、Wylie W. N. O、Zhaomin Hou

  DOI：10.1021/ja504995f

  日期：2014.9.3

  Cationic half-sandwich scandium alkyl complexes bearing monocyclopentadienyl ligands embedded in chiral binaphthyl backbones act as excellent catalysts for the enantioselective C-H bond addition of pyridines to various 1-alkenes, leading to formation of a variety of enantioenriched alkylated pyridine derivatives in high yields and excellent enantioselectivity (up to 98:2 er).
• Bis(binaphthylcyclopentadienyl)-derived metallocene peroxide complexes: Catalysts for the enantioselective epoxidation of unfunctionalized alkenes
  作者：Steven L. Colletti、Ronald L. Halterman

  DOI：10.1016/0022-328x(93)80387-q

  日期：1993.8

  The enantioselective catalytic epoxidation of unfunctionalized alkyl and aryl olefins was conducted using titanocene and niobocene peroxide complexes incorporating a C2-symmetrical binaphthylcyclopentadienyl ligand (BpDMCp). Enantiomeric excesses up to 20% and activities up to 55 turnovers were obtained with the application of our chiral bis(binaphthylcyclopen-tadienyl)-derived metallocenes. A significant decrease in the enantioselectivity for the epoxidation of trans-3-hexene was observed when the metal was changed from titanium to niobium in these binaphthyl-derived C2-symmetrical complexes. The preparation of the bis(binaphthylcyclopentadienyl)-chloroniobium peroxide complexes and bis(indenyl)chloroniobium peroxide is described.
• COLLETTI, STEVEN L.;HALTERMAN, RONALD L., TETRAHEDRON LETT., 30,(1989) N7, C. 3513-3516
  作者：COLLETTI, STEVEN L.、HALTERMAN, RONALD L.

  DOI：——

  日期：——