6A,6B-dideoxy-6A,6B-bis(tosyloxy)-β-cyclodextrin | 95475-64-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6A,6B-dideoxy-6A,6B-bis(tosyloxy)-β-cyclodextrin
• 英文别名: 6A6B-dideoxybis(tosyloxy)-β-cyclodextrin；6^A,6^B-ditosyl-β-CD；[(1S,3R,5R,6S,8R,10R,11S,13R,15R,16S,18R,20R,21S,23R,25R,26S,28R,30R,31S,33R,35R,36R,37R,38R,39R,40R,41R,42R,43R,44R,45R,46R,47R,48R,49R)-36,37,38,39,40,41,42,43,44,45,46,47,48,49-tetradecahydroxy-5,20,25,30,35-pentakis(hydroxymethyl)-10-[(4-methylphenyl)sulfonyloxymethyl]-2,4,7,9,12,14,17,19,22,24,27,29,32,34-tetradecaoxaoctacyclo[31.2.2.23,6.28,11.213,16.218,21.223,26.228,31]nonatetracontan-15-yl]methyl 4-methylbenzenesulfonate
• CAS: 95475-64-2
• 化学式: C₅₆H₈₂O₃₉S₂
• 分子量: 1443.38
• InChiKey: ZTTODFSDJIGVEV-DXCNPSTGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -11
• 重原子数：
  97
• 可旋转键数：
  13
• 环数：
  23.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  617
• 氢给体数：
  19
• 氢受体数：
  39

反应信息

• 作为反应物：
  描述：

  6A,6B-dideoxy-6A,6B-bis(tosyloxy)-β-cyclodextrin 在 sodium azide 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 3.0h， 以48%的产率得到6I,6II-diazido-6I,6II-dideoxy-cyclomaltoheptaose
  参考文献：
  名称：

  Unsymmetrically disubstituted .beta.-cyclodextrins of 6A,6X-dideoxy-6A-azido-6X-[(mesitylsulfonyl)oxy] derivatives

  摘要：

  DOI：

  10.1021/jo00222a042
• 作为产物：
  描述：

  β-环糊精 以9%的产率得到
  参考文献：
  名称：

  FUJITA, KAHEE;TAHARA, TSUTOMU;KOGA, TOSHITAKA, CHEM. LETT.,(1989) N, C. 821-824

  摘要：

  DOI：

文献信息

• Homo- and hetero-difunctionalized β-cyclodextrins: Short direct synthesis in gram scale and analysis of regiochemistry
  作者：Gábor Benkovics、Mihály Bálint、Éva Fenyvesi、Erzsébet Varga、Szabolcs Béni、Konstantina Yannakopoulou、Milo Malanga

  DOI：10.3762/bjoc.15.66

  日期：——

  The regioselective difunctionalization of cyclodextrins (CDs) leading to derivatives amenable to further transformations is a daunting task due to challenging purification and unambiguous characterization of the obtained regioisomers with similar physicochemical properties. The primary-side homo-difunctionalization of β-CD can lead to three regioisomers, while the hetero-difunctionalization can generate three pairs of pseudoenantiomers. Previously, approaches with several synthetic steps, expensive reagents, high purification demands and low yields of the products have been employed. Herein we present direct, short and efficient primary-side difunctionalization strategies featuring reproducibility, ease of product purification, scalability of the reactions and versatility of the substituents introduced. Specifically, the prepared ditosylated β-CDs were separated using preparative reversed-phase column chromatography and their structures were elucidated by NMR experiments. Azidation led to the corresponding pure diazido regioisomers. Direct monotosylation of 6-monoazido-β-CD or monoazidation of the single regioisomers 6^A,6^X-ditosyl-β-CDs afforded hetero-difunctionalized 6^A-monoazido-6^X-tosyl-β-CDs in significant yields. Overall, the single regioisomers, 6^A,6^X-ditosyl-, 6^A,6^X-diazido- and 6^A-monoazido-6^X-monotosyl-β-CD were prepared in one or two steps and purified in multigram scale thus opening the way towards further selective and orthogonal functionalizations of β-CD hosts.

  环糊精（CDs）的区域选择性双官能化导致衍生物易于进一步转化，由于所得到的区异构体具有相似的物理化学性质，挑战性的纯化和明确表征是一项艰巨的任务。β-CD的主侧同官能化可能导致三个区异构体，而异官能化可能产生三对伪对映体。以前采用了几个合成步骤、昂贵试剂、高纯化要求和低产率的方法。在这里，我们提出了直接、简短、高效的主侧双官能化策略，具有可重复性、易于产品纯化、反应可扩展性和引入的取代基的多功能性。具体地，制备的二对甲苯磺酰化β-CDs通过制备性反相柱色谱分离，并通过NMR实验阐明了它们的结构。偶氮化导致了相应的纯二叠氮区异构体。直接对6-单叠氮-β-CD进行单甲苯磺酰化或对单区异构体6A,6X-二对甲苯磺酰-β-CD进行单叠氮化，得到了产量可观的6A-单叠氮-6X-对磺酰-β-CD。总的来说，单区异构体6A,6X-二对甲苯磺酰-、6A,6X-二叠氮-和6A-单叠氮-6X-单对磺酰-β-CD可在一两个步骤中制备，并在多克级规模上纯化，从而为进一步选择性和正交功能化β-CD宿主打开了道路。
• The first topologically controlled synthesis of doubly bridged β-cyclodextrin dimers
  作者：De-Qi Yuan、Kazutaka Koga、Isao Kouno、Toshihiro Fujioka、Makoto Fukudome、Kahee Fujita

  DOI：10.1039/b613959k

  日期：——

  Reaction 6(A),6(B)-di(O-tosyl)-beta-cyclodextrin with Na(2)S in DMF gave the cis-dimer of beta-cyclodextrin in 21% isolated yield while the trans-dimer was not detected.

  在DMF中与Na（2）S反应的6（A），6（B）-二（O-甲苯磺酰基）-β-环糊精以21％的分离产率得到β-环糊精的顺二聚体，而反式二聚体不是检测到。
• Regiochemical Correlation between 6-O-Sulfonylated Cyclodextrins and 3-O-Sulfonylated Cyclodextrins via 3,6-Anhydrocyclodextrins
  作者：Kahee Fujita、Tsutomu Tahara、Yoshimitsu Egashira、Hatsuo Yamamura、Taiji Imoto、Toshitaka Koga、Toshihiro Fujioka、Kunihide Mihashi

  DOI：10.1246/cl.1988.705

  日期：1988.4.5

  (3R)-2,3-Anhydrocyclodextrins which were prepared from 3-O-sulfonylcyclodextrins were treated with aqueous alkali to give 3,6-anhydrocyclodextrins, which were prepared by the reaction of 6-O-sulfonylcyclodextrins with aqueous alkali. This regiochemical correlation was applicable to regioisomer determination of 3-O-disulfonylcyclodextrins on the basis of the regiochemistry of 6-O-disulfonates.

  由 3-O-磺酰环糊精制得的 (3R)-2,3-脱氢环糊精经水碱处理后得到 3,6-脱氢环糊精，而 3,6-脱氢环糊精是由 6-O-磺酰环糊精与水碱反应制得的。根据 6-O-二磺酸盐的区域化学性质，这种区域化学相关性适用于 3-O-二磺酰基环糊精的区域异构体测定。
• Flexibly capped β-cyclodextrins by the hydrogen-bonded nucleic acid base pair. The pH-control of binding ability by an on-off-switched capping
  作者：Katuyuki Nagai、Shigeo Ukal、Kenji Hayakawa、Ken Kanematsu

  DOI：10.1016/s0040-4039(00)98325-4

  日期：1985.1

  Preparation and characterization of flexibly capped β-cyclodextrins () by the hydrogen bonded nucleobase pair (i.e., adenine-thymine) are described.

  描述了通过氢键合的核碱基对（即腺嘌呤-胸腺嘧啶）制备和封端的柔性封端的β-环糊精（）。
• Specific preparation and structure determination of 3A,3C,3E-tri-O-sulfonyl-.beta.-cyclodextrin
  作者：Kahee Fujita、Tsutomu Tahara、Hatsuo Yamamura、Taiji Imoto、Toshitaka Koga、Toshihiro Fujioka、Kunihide Mihashi

  DOI：10.1021/jo00290a016

  日期：1990.2