3,7-anhydro-1,1,2,2-tetradehydro-1,2,6-trideoxy-6-C-ethynyl-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-D-glycero-D-gulo-octitol | 167646-61-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,7-anhydro-1,1,2,2-tetradehydro-1,2,6-trideoxy-6-C-ethynyl-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-D-glycero-D-gulo-octitol
• 英文别名: (2S,3S,4S,5R,6S)-3-ethynyl-2-(hydroxymethyl)-6-(2-trimethylsilylethynyl)-5-tri(propan-2-yl)silyloxyoxan-4-ol
• CAS: 167646-61-9
• 化学式: C₂₂H₄₀O₄Si₂
• 分子量: 424.728
• InChiKey: FYPOPHGVGBSYFY-TWGBQZSLSA-N

物化性质

• 熔点：
  136-138 °C
• 沸点：
  463.5±45.0 °C(predicted)
• 密度：
  1.00±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  58.9
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3,7-anhydro-1,1,2,2-tetradehydro-1,2,6-trideoxy-6-C-ethynyl-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-D-glycero-D-gulo-octitol 在 N-溴代丁二酰亚胺(NBS) 、 silver trifluoroacetate 作用下， 以 丙酮 为溶剂， 反应 6.0h， 以75%的产率得到3,7-anhydro-1,2,6-trideoxy-6-C-(bromoethynyl)-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-D-glycero-D-gulo-oct-1-ynitol
  参考文献：
  名称：

  Oligosaccharide Analogues of Polysaccharides, Part 16, Cross-Coupling of Partially Protected Dialkynyl Monosaccharides

  摘要：

  The dependency of the cross-coupling of orthogonally C-protected dialkynyl monosaccharides on the nature of the coupling partners has been studied, The required dialkyne 5 was synthesized from levoglucosan in six steps and 39% overall yield and transformed into 7 10, 12, 13, and 14 by orthogonal C-deprotection and bromination (Scheme 1). Optimization of the conditions of their cross-coupling to 16 showed that yields were higher for the coupling of the propargylic bromoalkyne 10 than for the homopropargylic bromoalkyne 14 (Scheme 2). Deprotection of 16 gave the nano-crystalline dimer 20. To obtain more highly crystalline products, the monomers 7 and 13 were coupled with 1-iodo-4-nitrobenzene to the arylated monomers 21 and 24 (Scheme 3). The 4-NO2C6H4, substituent lowered the yield of the dimerizations to the mono- and diarylated dimers 26-28 (Scheme 4) but had no effect on crystallinity.

  DOI：

  10.1002/(sici)1522-2675(19990210)82:2<143::aid-hlca143>3.0.co;2-0
• 作为产物：
  描述：

  3,7-anhydro-1,1,2,2-tetradehydro-1,2,6-trideoxy-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-6-C-<2-(trimethylsilyl)ethyl>-D-glycero-D-gulo-octitol 在 silver(I) nitrite 作用下， 以 甲醇 、 水 为溶剂， 反应 3.0h， 以96%的产率得到3,7-anhydro-1,1,2,2-tetradehydro-1,2,6-trideoxy-6-C-ethynyl-4-O-(triisopropylsilyl)-1-C-(trimethylsilyl)-D-glycero-D-gulo-octitol
  参考文献：
  名称：

  多糖的寡糖类似物。第2部分。单糖衍生的单体和二聚体的区域选择性脱保护

  摘要：

  在ME 3的SiC（1）的双- （三甲基硅烷基）的键乙炔anhydroalditol 2被选择性地用BuLi切割以产生3 / 4，而硝酸银2 / KCN在MeOH裂解我3的SiC（2'）键，导致5（方案1）。两个Me 3 Si基团都用NaOH在MeOH中的溶液（7）除去，（i-Pr）3 Si基团用HCl水溶液选择性地裂解。MeOH（6）；m / z（MH）。用Bu 4 NF（8）除去所有的甲硅烷基取代基。乙酰分解将9转化为13，将其脱甲硅烷基以14，而硫解的9导致了混合物11 / 12。四乙酸酯14也已经从9经由10获得。的任一氧化二聚化3或5，或它们的混合物的3 / 5的产率只有同二聚体15和16（方案2）; 用AgNO 2 / KCN处理16能产生17，脱保护的过程比裂解Me 3 SiC（2'）基团慢得多。2。的iodoalkyne 20，具有所需的交叉耦合5根据Cadiot-Chodkiewicz，的制备是通过脱保护3

  DOI：

  10.1002/hlca.19950780117

文献信息

• Oligosaccharide Analogues of Polysaccharides. Part 1. Concept and synthesis of monosaccharide-derived monomers
  作者：Jawad Alzeer、Chengzhi Cai、Andrea Vasella

  DOI：10.1002/hlca.19950780122

  日期：1995.2.8

  properties of polysaccharides by comparing them to a series of systematically modified oligosaccharide analogues where some or all of the glycosidic O-atoms are replaced by buta-1,3-diyne-1,4-diyl groups. This group is long enough to interrupt the interresidue H-bonds, is chemically versatile, and allows a binomial synthesis. Several approaches to the simplest monomeric unit required to make analogues of cellulose

  建议通过与一系列系统修饰的寡糖类似物（其中一些或所有糖苷O原子被buta-1,3-diyne取代）进行比较，研究残基间H键对多糖结构和性质的影响。 -1，4-二基。该基团足够长以中断残基间的氢键，在化学上是多用途的，并允许二项式合成。描述了制备纤维素类似物所需的最简单单体单元的几种方法。在第一种方法中，通过2和三苄基醚3将烯丙基α-D-吡喃半乳糖苷（1）转化为三氟甲磺酸酯4（方案2）。被氰化物取代（5–7），然后用DIBAH还原，可高产率生成醛9，按照Corey-Fuchs程序（方案3）将其转化为二溴烯烃10和炔烃11。炔烃经12脱保护或直接与半缩醛13脱保护。氧化至内酯14，然后添加三甲基甲硅烷基乙炔酸锂Me 3 SiCCLi / CeCl 3（15）和还原性脱羟基，得到二甲苯二炔16。转化所需的大量Pd催化剂11 13通过将二溴代烯烃10（17 18）脱醛，随后氧化为内酯19，将Me 3
• Synthesis of Substituted Mono- and Diindole C-Nucleoside Analogues from Sugar Terminal Alkynes by Sequential Sonogashira/Heteroannulation Reaction
  作者：Fuyi Zhang、Delong Mu、Liming Wang、Pengfei Du、Fen Han、Yufen Zhao

  DOI：10.1021/jo501488x

  日期：2014.10.17

  The synthesis of substituted mono- and diindole C-nucleoside analogues has been achieved in good to excellent yields by sequential Sonogashira coupling/NaAuCl4-catalyzed heteroannulation reactions of substituted 2-iodoanilines with various sugar terminal alkynes in one pot. The method is general, mild, and efficient and suitable for a wide range of sugar substrates, and 42 examples are given. The amino

  通过在一个罐中通过顺序的Sonogashira偶联/ NaAuCl 4催化的取代2-碘苯胺与各种糖末端炔烃的杂环化反应，已经以良好或优异的产率实现了取代的单和二吲哚C-核苷类似物的合成。该方法通用，温和，有效，适用于多种糖底物，给出了42个实例。取代的2-碘苯胺的氨基是未保护的。糖末端炔烃包括呋喃糖苷，吡喃糖苷和具有游离羟基的无环糖苷，敏感的功能性取代基和具有不同空间位阻的各种保护基。
• Influence of an Ethynyl or a Buta-1,3-diynyl Group on the Chemical Shifts of Hydroxy Groups of Glucopyranoses
  作者：Bruno Bernet、Roland Bürli、Jinwang Xu、Andrea Vasella

  DOI：10.1002/1522-2675(200206)85:6<1800::aid-hlca1800>3.0.co;2-s

  日期：2002.6

  of the OH chemical shifts for 1-mono-, 4-mono-, and 1,4-diethynylated and 1,4-buta-1,3-diynylated glucopyranoses with those of β-D-glucopyranose (1) identified characteristic increments for the OH (downfield) shifts of the alkynylated glucopyranoses in (D6)DMSO solution. For ethynylated derivatives, the increments vary from 0.05 ppm for HOC(6) (replacement of HOC(1) by an axial ethynyl group) to 0.5 ppm

  1-单-、4-单-和 1,4-二乙炔化和 1,4-丁-1,3-二炔化吡喃葡萄糖与 β-D-吡喃葡萄糖 (1) 的 OH 化学位移的比较确定了特征（D6）DMSO溶液中炔基化吡喃葡萄糖的OH（低场）位移增量。对于乙炔化衍生物，增量从 HOC(6) 的 0.05 ppm（用轴向乙炔基替换 HOC(1)）到 HOC(2) 的 0.5 ppm（用赤道乙炔基替换 HOC(1)）不等。buta-1,3-diynylated 衍生物的增量更大，从 0.1 到 0.7 ppm 不等。在 C(1) 而不是 C(4) 的这种替代对邻位 OH 基团转变的影响更强。
• Oligosaccharide Analogues of Polysaccharides, Part 17, Synthesis and Characterization of a Hexadecamer: Evidence for the Essential Structural Role of the Intramolecular, Interresidue C(3)−OH⋅⋅⋅O−C(5) Hydrogen Bond in Celluloses
  作者：Tanja Verena Bohner、Olav-Sven Becker、Andrea Vasella

  DOI：10.1002/(sici)1522-2675(19990210)82:2<198::aid-hlca198>3.0.co;2-y

  日期：1999.2.10

  The hexadecamer 63 dissolves readily in DMSO and shows no sign of association, in agreement with the essential structural role of the intramolecular, interresidue C(3)-OH ... O-C(5) H-bond of celluloses, MM3 Calculations predict a rod-like shape for the cello-oligosaccharides In agreement with this, nanocrystalline domains of parallel chains are observed by high-resolution electron microscopy (HREM) for 54 and 63 on carbon-coated copper grids. For the synthesis of the hexadecamer 54, we studied the influence of protecting groups on the cross-coupling of acetyleno-oligosaccharides and on their solubility (Scheme 2). The octamer 12 derived from the minimally O-protected monomer 2 is insoluble, while the methoxymethyl- and triisopropysilyl-protected hexadecamer 54 prepared in twelve steps from the dimer 41 (Scheme 4), is readily soluble in a variety of solvents. O- and C-deprotection of 54 led in four steps and in 76% yield to the hexadecamer 63 (Schemes 5 and 6). There is only a small difference of spectroscopic properties between the protected octamer 50 and hexadecamer 54, and, similarly, between the unprotected octamer 64 and hexadecamer 63 (Fig. 3).