5,6:5''',6'''-Bis[(1R,5R)-(-)-pineno]-2,2':6',2'':6'',2'''-quaterpyridine | 199852-82-9

• 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: 5,6:5''',6'''-Bis[(1R,5R)-(-)-pineno]-2,2':6',2'':6'',2'''-quaterpyridine
• 英文别名: (1R,9R)-5-[6-[6-[(1R,9R)-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-trien-5-yl]pyridin-2-yl]pyridin-2-yl]-10,10-dimethyl-6-azatricyclo[7.1.1.02,7]undeca-2(7),3,5-triene
• CAS: 199852-82-9
• 化学式: C₃₄H₃₄N₄
• 分子量: 498.671
• InChiKey: HBQQLPUTMULXTA-CHOVIJNXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.5
• 重原子数：
  38
• 可旋转键数：
  3
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tetrakis(actonitrile)copper(I) hexafluorophosphate 、 5,6:5''',6'''-Bis[(1R,5R)-(-)-pineno]-2,2':6',2'':6'',2'''-quaterpyridine 以 乙腈 为溶剂， 以96%的产率得到
  参考文献：
  名称：

  手性四吡啶的螺旋配合物 - 单核 CuII 和双核 CuI 配合物

  摘要：

  通过将手性配体 L1-4 与 CuI 和 CuII 前体反应制备了两个系列的手性螺旋铜-四吡啶配合物。CuII 配合物 [Cu(L)(H2O)(ClO4)2] 或 [Cu(L)(ClO4)2] 通过 ESI-MS、元素分析和 CD 光谱进行研究，而 CuI 配合物 [Cu2 (L)2](PF6)2，通过核磁共振、ESI-MS、元素分析和CD 光谱检查。[Cu(L1)(H2O)(ClO4)](ClO4)和[Cu(L3)(ClO4)2]的晶体结构由X射线衍射确定。它们是单体的、扭曲的八面体配合物，在四个赤道位置配位四联吡啶配体，在顶端位置配位一或两个高氯酸盐。还确定了 [Cu(L1m)(H2O)(ClO4)](ClO4) 的晶体结构，它具有非手性四联吡啶配体 L1m，即 L1 的内消旋形式。[Cu(L1)(H2O)(ClO4)](ClO4) 和 [Cu(L1m)(H2O)(ClO4)](ClO4)

  DOI：

  10.1002/ejic.201100630
• 作为产物：
  描述：

  pinocarvone 、 6,6'-Bis(1-pyridinioacetyl)-2,2'-bipyridine diiodide 在 ammonium acetate 、 乙酸酐 、 溶剂黄146 作用下， 以81%的产率得到5,6:5''',6'''-Bis[(1R,5R)-(-)-pineno]-2,2':6',2'':6'',2'''-quaterpyridine
  参考文献：
  名称：

  Stereoselective Double-Helicate Assembly from Chiral 2,2′:6′,2″:6″,2′′′-Quaterpyridines and Tetrahedral Metal Centres

  摘要：

  A pair of chiral 2,2':6',2 ":6 ",2'''-quaterpyridine ligands 1 and 2 have been prepared and shown to diastereoselectively assemble double-helical coordination compounds. The complexation of 1 or 2 with copper(I) or silver(I) leads to dinuclear double helicates [M-2(L)(2)](2+) with high diastereoselectivity [diastereomeric excess (d.e.) greater than or equal to 96%] for the formation of P or M helicates. Circular dichroism (CD) studies of the helicates in solution reveal intense activity in the region of 320-328 nm that is diagnostic of P or M helical chirality. On the basis of the CD spectra it is proposed that the dominant diastereomers with 1 possess P helicity, whilst those with 2 possess M helical chirality. These proposals have been confirmed by solid-state structural determinations of the dominant diastereomers of [Cu-2(1)(2)][PF6](2). 2MeCN. [Cu-2(2)(2)][PF6](2). 2MeCN and [Ag-2(1)(2)][PF6](4). 0.33 H2O. Redistribution reactions of dicopper(I) and disilver(I) helicates lead to the stereoselective assembly of heterodinuclear helicates, whereas the reaction of [Cu-2(1)(2)](2+) with [Cu-2(2)(2)](2+) leads to the formation of the heterochiral, heterostranded species [Cu-2(1)(2)](2-).

  DOI：

  10.1002/(sici)1521-3765(19990604)5:6<1862::aid-chem1862>3.0.co;2-g

文献信息

• Stereoselective Formation of Helical Binuclear Metal Complexes: Synthesis, Characterization, and Crystal Structures of Chiral Bis-Rhenium(I) Quaterpyridine Complexes
  作者：Ho-Lun Yeung、Wai-Yeung Wong、Chun-Yuen Wong、Hoi-Lun Kwong

  DOI：10.1021/ic802249f

  日期：2009.5.4

  By 1H and 13C NMR analysis, all the crude complexes consisted of a pair of stereoisomers. Sterically more demanding ligand L4 induced a higher ratio (80:20) than L1−3 (about 56:44). Stereochemically pure complexes could be obtained by recrystallization in CH2Cl2. X-ray crystallographic analysis of single crystals from purified complexes showed a single-stranded helical structure with a bridging ligand

  一系列单链螺旋的Re（I）配合物的，式[重2（大号）溴2（CO）6 ]中，通过反应制备[的Re（CO）5 BR]与手性quaterpyridines L1 - 4。通过1 H和13 C NMR分析，所有粗配合物均由一对立体异构体组成。空间更苛刻的配体L4诱导比更高的比率（80:20）L1 - 3（约56:44）。在CH 2 Cl 2中重结晶可得到立体化学纯的配合物。纯化的复合物的单晶的X射线晶体学分析显示，单链螺旋结构具有桥接配体，该配体包裹在两个扭曲的八面体，金属上，这两个八面体f金属在fac配位中均具有一个溴化物配体和三个羰基配体。螺旋核心是通过广泛的非共价静电相互作用建立的，手性信息通过这些相互作用从配体传递到螺旋上。通过CD光谱研究了溶液的行为，强的棉花效应证实了溶液中螺旋结构的完整性。提议通过溴原子和桥连配体的取代基之间的空间相互作用来诱导螺旋体的非对映选择性。
• Baum, Gerhard; Constable, Edwin C.; Fenske, Dieter, Chemical Communications, 1997, # 21, p. 2043 - 2044
  作者：Baum, Gerhard、Constable, Edwin C.、Fenske, Dieter、Kulke, Torsten

  DOI：——

  日期：——
• Helical Complexes of Chiral Quaterpyridines – Mononuclear Cu ^II and Dinuclear Cu ^I Complexes
  作者：Ho‐Lun Yeung、Kiu‐Chor Sham、Wai‐Yeung Wong、Chun‐Yuen Wong、Hoi‐Lun Kwong

  DOI：10.1002/ejic.201100630

  日期：2011.11

  series of chiral helical copper–quaterpyridine complexes were prepared by reacting chiral ligands L1–4 with CuI and CuII precursors. The CuII complexes, [Cu(L)(H2O)(ClO4)2] or [Cu(L)(ClO4)2], were studied by ESI-MS, elemental analysis, and CD spectroscopy, and the CuI complexes, [Cu2(L)2](PF6)2, were examined by NMR, ESI-MS, elemental analysis, and CD spectroscopy. The crystal structures of [Cu(L1)(H2O)(ClO4)](ClO4)

  通过将手性配体 L1-4 与 CuI 和 CuII 前体反应制备了两个系列的手性螺旋铜-四吡啶配合物。CuII 配合物 [Cu(L)(H2O)(ClO4)2] 或 [Cu(L)(ClO4)2] 通过 ESI-MS、元素分析和 CD 光谱进行研究，而 CuI 配合物 [Cu2 (L)2](PF6)2，通过核磁共振、ESI-MS、元素分析和CD 光谱检查。[Cu(L1)(H2O)(ClO4)](ClO4)和[Cu(L3)(ClO4)2]的晶体结构由X射线衍射确定。它们是单体的、扭曲的八面体配合物，在四个赤道位置配位四联吡啶配体，在顶端位置配位一或两个高氯酸盐。还确定了 [Cu(L1m)(H2O)(ClO4)](ClO4) 的晶体结构，它具有非手性四联吡啶配体 L1m，即 L1 的内消旋形式。[Cu(L1)(H2O)(ClO4)](ClO4) 和 [Cu(L1m)(H2O)(ClO4)](ClO4)
• Stereoselective Double-Helicate Assembly from Chiral 2,2′:6′,2″:6″,2′′′-Quaterpyridines and Tetrahedral Metal Centres
  作者：Gerhard Baum、Edwin C. Constable、Dieter Fenske、Catherine E. Housecroft、Torsten Kulke

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1862::aid-chem1862>3.0.co;2-g

  日期：1999.6.4

  A pair of chiral 2,2':6',2 ":6 ",2'''-quaterpyridine ligands 1 and 2 have been prepared and shown to diastereoselectively assemble double-helical coordination compounds. The complexation of 1 or 2 with copper(I) or silver(I) leads to dinuclear double helicates [M-2(L)(2)](2+) with high diastereoselectivity [diastereomeric excess (d.e.) greater than or equal to 96%] for the formation of P or M helicates. Circular dichroism (CD) studies of the helicates in solution reveal intense activity in the region of 320-328 nm that is diagnostic of P or M helical chirality. On the basis of the CD spectra it is proposed that the dominant diastereomers with 1 possess P helicity, whilst those with 2 possess M helical chirality. These proposals have been confirmed by solid-state structural determinations of the dominant diastereomers of [Cu-2(1)(2)][PF6](2). 2MeCN. [Cu-2(2)(2)][PF6](2). 2MeCN and [Ag-2(1)(2)][PF6](4). 0.33 H2O. Redistribution reactions of dicopper(I) and disilver(I) helicates lead to the stereoselective assembly of heterodinuclear helicates, whereas the reaction of [Cu-2(1)(2)](2+) with [Cu-2(2)(2)](2+) leads to the formation of the heterochiral, heterostranded species [Cu-2(1)(2)](2-).