1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-glucopyranose | 917616-26-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-glucopyranose
• 英文别名: acetyl 3,4,6-tri-O-acetyl-2-deoxy-2-N-trichloroethoxysulfamido-β-D-glucopyranoside；[(2R,3S,4R,5R,6S)-3,4,6-triacetyloxy-5-(2,2,2-trichloroethoxysulfonylamino)oxan-2-yl]methyl acetate
• CAS: 917616-26-3
• 化学式: C₁₆H₂₂Cl₃NO₁₂S
• 分子量: 558.775
• InChiKey: DKIGBJBOAPFAJC-KJWHEZOQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  33
• 可旋转键数：
  13
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  178
• 氢给体数：
  1
• 氢受体数：
  13

反应信息

• 作为反应物：
  描述：

  1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-glucopyranose 在 氨 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 0.25h， 以81%的产率得到[(2R,3S,4R,5R,6S)-3,4-diacetyloxy-6-hydroxy-5-(2,2,2-trichloroethoxysulfonylamino)oxan-2-yl]methyl acetate
  参考文献：
  名称：

  Effective protection of the N-sulfate of glucosamine derivatives with the 2,2,2-trichloroethyl group

  摘要：

  The 2,2,2-trichloroethyl (TCE) group was utilized as the first protecting group for N-sulfates (chlorosulfuric acid TCE ester, Et3N, DMAP, DMF). Glycosylation with 3,4,6-tri-O-acetyl-N-trichloroethylsulfuryl-alpha-D-glucosaminosyl trichloroacetimidate provided the corresponding beta-glucosaminosides stereoselectively and in excellent yields. The TCE protection stayed stable under a variety of conditions for the manipulation of other protecting groups, and was readily removable with zinc in the presence of ammonium chloride in methanol. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.12.132
• 作为产物：
  描述：

  2,2,2-三氯乙基氯磺酸酯 、 1,3,4,6-四-O-乙酰基-2-氨基-2-脱氧-Β-D-葡萄糖盐酸盐 在 4-二甲氨基吡啶 、 三乙胺 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 以82%的产率得到1,3,4,6-tetra-O-acetyl-2-deoxy-2-(2,2,2-trichloroethoxysulfonyl)amido-β-D-glucopyranose
  参考文献：
  名称：

  Effective protection of the N-sulfate of glucosamine derivatives with the 2,2,2-trichloroethyl group

  摘要：

  The 2,2,2-trichloroethyl (TCE) group was utilized as the first protecting group for N-sulfates (chlorosulfuric acid TCE ester, Et3N, DMAP, DMF). Glycosylation with 3,4,6-tri-O-acetyl-N-trichloroethylsulfuryl-alpha-D-glucosaminosyl trichloroacetimidate provided the corresponding beta-glucosaminosides stereoselectively and in excellent yields. The TCE protection stayed stable under a variety of conditions for the manipulation of other protecting groups, and was readily removable with zinc in the presence of ammonium chloride in methanol. (c) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2007.12.132

文献信息

• Rh-catalyzed alkene oxidation: a highly efficient and selective process for preparing N-alkoxysulfonyl aziridines
  作者：Kiran Guthikonda、Paul M. Wehn、Brian J. Caliando、J. Du Bois

  DOI：10.1016/j.tet.2006.07.099

  日期：2006.12

  Unique alkoxysulfonyl aziridine heterocycles were prepared through selective intra- and intermolecular alkene oxidation reactions. These methods are general and perform efficiently at low Rh-catalyst loadings (1–2 mol %) with only a slight excess of an inexpensive commercial oxidant, PhI(OAc)2. For intermolecular processes, trichloroethylsulfamate was identified as a novel and markedly effective N-atom

  通过选择性的分子内和分子间烯烃氧化反应制备了独特的烷氧基磺酰基氮丙啶杂环。这些方法是通用的，并且在少量Rh催化剂负载量（1-2 mol％）下有效执行，仅略有过量的廉价商业氧化剂PhI（OAc）2。对于分子间方法，三氯乙基氨基磺酸盐被确定为一种新型且显着有效的N原子源，可在有限量的烯烃底物条件下进行反应。氮丙啶产物易于开亲核开环；这些方法具有区域选择性，可通过直接添加Me 2 SO来制备包括α-氨基酮在内的多官能胺。
• Novel stereocontrolled amidoglycosylation of alcohols with acetylated glycals and sulfamate ester
  作者：Teiichi Murakami、Yukari Sato、Kyoko Yoshioka、Mutsuo Tanaka

  DOI：10.1039/c4ra02367f

  日期：——

  A regio- and stereo-controlled, one-pot amidoglycosylation of alcohols has been achieved using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene in the presence of a rhodium(ii) catalyst.

  一种区域和立体控制的一锅法醇的酰胺基糖苷化反应已经通过在铑（II）催化剂存在下使用O-乙酰基基卡尔、三氯乙氧基磺酰胺和碘苯酚实现。
• Convenient stereocontrolled amidoglycosylation of alcohols with acetylated glycals and trichloroethoxysulfonamide
  作者：Teiichi Murakami、Yukari Sato、Kyoko Yoshioka、Mutsuo Tanaka

  DOI：10.1016/j.carres.2016.09.001

  日期：2016.11

  of alcohols has been developed using O-acetylated glycals, trichloroethoxysulfonamide, and iodosobenzene. This one-pot amidoglycosylation was applied to a variety of primary and secondary alcohols to afford the beta-O-glycosides with acceptable yields up to 84%. The reaction would proceed via stereoselective intermolecular aziridination of the glycal from the alpha-face followed by SN2 reaction with

  使用O-乙酰基化的糖，三氯乙氧基磺酰胺和碘代苯，已经开发出了区域和立体控制的铑（II）催化的醇酰胺糖基化反应。将这种一锅式酰胺基糖基化反应应用于各种伯醇和仲醇，以高达84％的可接受收率得到β-O-糖苷。该反应将通过α面的糖的立体选择性分子间叠氮化进行，然后与β面的C-1处的醇进行SN2反应，仅得到1,2：2,3-二-反式取代的异构体。
• <i>O</i>- and <i>N</i>-Sulfations of Carbohydrates Using Sulfuryl Imidazolium Salts
  作者：Laura J. Ingram、Ahmed Desoky、Ahmed M. Ali、Scott D. Taylor

  DOI：10.1021/jo9014112

  日期：2009.9.4

  A series of sulfuryl imidazolium salts (SISs) were prepared and examined as reagents for incorporating trichloroethyl-protected sulfate esters into carbohydrates. The SIS that contained a 1,2-dimethylimidazolium moiety (SIS 9) proved to be a superior sulfating compared to SISs bearing no alkyl groups or bulkier alkyl groups on the imidazolium ring. Difficult O-sulfations that required prolonged reaction times and a large excess of the SIS bearing a 1-methylimidazolium group (SIS 5) were achieved in high yield using less than half the amount of SIS 9 in less time. Certain N-sulfated compounds that were practically inaccessible using SIS 5 were obtained in excellent yield using SIS 9.