6(A),6(B)-di-O-methylsulfonyl-2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(D),6(E),6(F)-hexadeca-O-methyl-α-CD | 139622-74-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6(A),6(B)-di-O-methylsulfonyl-2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(D),6(E),6(F)-hexadeca-O-methyl-α-CD
• 英文别名: 6¹,6²-Di-O-methylsulfonyl-cG₆ permethylate
• CAS: 139622-74-5
• 化学式: C₅₄H₉₆O₃₄S₂
• 分子量: 1353.47
• InChiKey: VKAGBPNSTAAWIX-PIGKAOJQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.62
• 重原子数：
  90.0
• 可旋转键数：
  26.0
• 环数：
  22.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  345.18
• 氢给体数：
  0.0
• 氢受体数：
  34.0

反应信息

• 作为反应物：
  描述：

  6(A),6(B)-di-O-methylsulfonyl-2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(D),6(E),6(F)-hexadeca-O-methyl-α-CD 在 sodium iodide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以70.4%的产率得到6¹,6²-Dideoxy-6¹,6²-diiodo-cG₆ permethylate
  参考文献：
  名称：

  Preparation of di-O-triphenylmethyl-(trityl)-cyclomalto-hexaoses and -cyclomaltoheptaoses and characterization of three positional isomers of each by the “hex-5-enose degradation”

  摘要：

  Regioisomeric 6l,6n-di-O-trityl-cyclomaltohexaoses (cG6s) or -cyclomaltoheptaoses (cG7s) were prepared by the reaction of cyclomaltohexaose (1, cG6) or cylomaltoheptaose (5, cG7) with chlorotriphenylmethane methane in pyridine and isolation by h.p.l.c. The regiochemical determination of each three ditrityl-substituted substituted derivatives has been accomplished by the "hex-5-enose degradation", followed by measurement of their f.a.b.-mass spectra.

  DOI：

  10.1016/0008-6215(92)80001-h
• 作为产物：
  描述：

  甲基磺酰氯 、 2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(D),6(E),6(F)-hexadeca-O-methyl-α-CD 在 吡啶 作用下， 以83.1%的产率得到6(A),6(B)-di-O-methylsulfonyl-2(A),2(B),2(C),2(D),2(E),2(F),3(A),3(B),3(C),3(D),3(E),3(F),6(C),6(D),6(E),6(F)-hexadeca-O-methyl-α-CD
  参考文献：
  名称：

  Preparation of di-O-triphenylmethyl-(trityl)-cyclomalto-hexaoses and -cyclomaltoheptaoses and characterization of three positional isomers of each by the “hex-5-enose degradation”

  摘要：

  Regioisomeric 6l,6n-di-O-trityl-cyclomaltohexaoses (cG6s) or -cyclomaltoheptaoses (cG7s) were prepared by the reaction of cyclomaltohexaose (1, cG6) or cylomaltoheptaose (5, cG7) with chlorotriphenylmethane methane in pyridine and isolation by h.p.l.c. The regiochemical determination of each three ditrityl-substituted substituted derivatives has been accomplished by the "hex-5-enose degradation", followed by measurement of their f.a.b.-mass spectra.

  DOI：

  10.1016/0008-6215(92)80001-h

文献信息

• Aza-capped cyclodextrins for intra-cavity metal complexation
  作者：D. Sechet、Z. Kaya、T.-A. Phan、M. Jouffroy、E. Bentouhami、D. Armspach、D. Matt、L. Toupet

  DOI：10.1039/c7cc06434a

  日期：——

  reacting the soft nitrogen nucleophile 2-nitrobenzenesulfonamide with either A,B-dimesylated CDs in basic media or their diol analogues under Mitsunobu reaction conditions followed by deprotection with thiophenol. A methyl pyridine substituent was grafted on the N atom of these secondary amines. When built on an α-CD scaffold, the resulting tertiary amine no longer undergoes nitrogen inversion at room temperature

  通过在Mitsunobu反应条件下使软氮亲核试剂2-硝基苯磺酰胺与A，B-二甲磺化CD或它们的二醇类似物在Mitsunobu反应条件下反应，然后用硫酚脱保护，可以高产率获得氮杂封端的甲基化环糊精（CD）。甲基吡啶取代基接枝在这些仲胺的N原子上。当在α-CD支架上构建时，所得叔胺在室温下不再经历氮转化，而充当封闭配体，为腔内金属络合开辟了道路，并促进了超分子螺旋的形成。
• Diastereospecific synthesis of phosphinidene-capped cyclodextrins leading to “introverted” ligands
  作者：Eric Engeldinger、Laurent Poorters、Dominique Armspach、Dominique Matt、Loïc Toupet

  DOI：10.1039/b315802k

  日期：——

  α-Cyclodextrins (α-CDs) containing “PPh” units which cap the primary face of the CD were obtained in high yield by reaction of Li2PPh with A,B- or A,C-dimesylated and A,B,D,E-tetramesylated precursors; the resulting phosphines are diastereomerically pure and constitute valuable precursors for the synthesis of metallo-cavitands.

  通过 Li2PPh 与 A,B-或 A,C-二甲酰化和 A,B,D,E-四甲酰化的前体反应，高产率地获得了含有âPPhâ单元的α-环糊精（α-CDs），âPPhâ单元位于 CD 的主面。
• Sulfur-capped cyclodextrins: a new class of cavitands with extroverted as well as introverted donor functionalities
  作者：Belkacem Benmerad、Pascaline Clair、Dominique Armspach、Dominique Matt、Fadila Balegroune、Loic Toupet

  DOI：10.1039/b603400d

  日期：——

  Ansa-cyclodextrins were obtained in high yields by reaction of sodium sulfide with A,B-di- or A,B,D,E-tetramesylated α-CD precursors; the resulting thiocavitands are suitable for forming nanotubular molecules, as well as for hosting metal-organic fragments.

  通过硫化钠与A,B-二甲基或A,B,D,E-四甲基α-CD前体的反应，可以高产量地获得Ansa-环糊精；所得的硫代卡维坦可用于形成纳米管分子，以及容纳金属有机片段。
• A cavity-shaped <i>cis</i>-chelating P,N ligand for highly selective nickel-catalysed ethylene dimerisation
  作者：Yang Li、Katrin Pelzer、Damien Sechet、Geordie Creste、Dominique Matt、Pierre Braunstein、Dominique Armspach

  DOI：10.1039/d2dt01553f

  日期：——

  exclusive formation of 1 : 1 ligand/metal complexes. In MX2 complexes, one of the two halido ligands is forced to reside inside the CD hollow while the second one is pointing outside. Unlike its cavity-free analogue, a Ni(II) complex of the CD ligand is a highly selective precatalyst for ethylene dimerisation (96% C4 selectivity with up to 95% of 1-butene within the C4 fraction).

  螯合 P,N 配体中全甲基化 α-环糊精 (α-CD) 空腔的存在促进了 1:1 配体/金属复合物的排他性形成。在 MX 2配合物中，两个卤代配体之一被迫驻留在 CD 空心内，而第二个则指向外部。与其无空腔类似物不同，CD 配体的 Ni( II ) 配合物是乙烯二聚化的高选择性预催化剂（C 4部分中高达 95% 的 1-丁烯选择性高达96% ）。
• Stabilization of Luminescent Mononuclear Three‐Coordinate Cu^I Complexes by Two Distinct Cavity‐Shaped Diphosphanes Obtained from a Single α‐Cyclodextrin Precursor
  作者：Tuan‐Anh Phan、Matthieu Jouffroy、Dominique Matt、Nicola Armaroli、Alejandra Saavedra Moncada、Elisa Bandini、Béatrice Delavaux‐Nicot、Jean‐François Nierengarten、Dominique Armspach

  DOI：10.1002/chem.202302750

  日期：2024.2

  Slightly different reaction conditions afforded two distinct cavity‐shaped cis‐chelating diphosphanes from the same starting materials, namely diphenyl(2‐phosphanylphenyl)phosphane and an α–cyclodextrin‐derived dimesylate. Thanks to their metal‐confining properties, the two diphosphanes form only mononuclear [CuX(PP)] complexes (X=Cl, Br, or I) with the tricoordinated metal ion located just above the center of the cavity. The two series of Cu^I complexes display markedly different luminescence properties that are both influenced by the electronic properties of the ligand and the unique steric environment provided by the cyclodextrin (CD) cavity. The excited state lifetimes of all complexes are significantly longer than those of the cavity‐free analogues suggesting peculiar electronic effects that affect radiative deactivation constants. The overall picture stemming from absorption and emission data suggests close‐lying charge‐transfer (MLCT, XLCT) and triplet ligand‐centered (LC) excited states.

  摘要略微不同的反应条件可从相同的起始原料（即二苯基（2-膦酰基苯基）膦烷和α-环糊精衍生的二甲膦酸酯）得到两种不同的空腔形顺式螯合二膦。由于这两种二膦烷的金属封闭特性，它们只能形成单核[CuX(PP)]配合物（X=Cl、Br 或 I），三配位金属离子位于空腔中心的正上方。这两个系列的 CuI 复合物显示出明显不同的发光特性，这既受到配体电子特性的影响，也受到环糊精（CD）空腔提供的独特立体环境的影响。所有复合物的激发态寿命都明显长于无空腔类似物，这表明它们具有影响辐射失活常数的特殊电子效应。从吸收和发射数据得出的总体情况表明，存在近邻电荷转移（MLCT、XLCT）和三重配体中心（LC）激发态。