Ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside | 116455-00-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: Ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
• 英文别名: (2R,3R,6S)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-6-ethoxy-3,6-dihydro-2H-pyran-3-ol
• CAS: 116455-00-6
• 化学式: C₁₄H₂₈O₄Si
• 分子量: 288.459
• InChiKey: JSOXSNXLZDWGKP-UPJWGTAASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside 在 四溴化碳 、 四丁基氟化铵 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 ethyl 4-bromo-2,3,4-trideoxy-α-D-erythro-hex-2-enopyranoside
  参考文献：
  名称：

  水介质中铟促进的 Barbier 型烯丙基化：获得 2-C- 和 4-C-支链糖的新途径

  摘要：

  在 2-bromo-4-enopyranoside (3) 和 4-bromo-2-enopyranosides（2β、6α 和 6β）的水性介质中，铟促进的 Barbier 型烯丙基化为不同的 2-C-支链糖提供了新途径（7 , 11, 13) 和 4-C-支链糖 (18)。此外，除了这些 C 支糖的合成和表征之外，还讨论了这些反应的机理方面。

  DOI：

  10.1002/1615-4169(200206)344:3/4<319::aid-adsc319>3.0.co;2-s
• 作为产物：
  描述：

  ethyl 4,6-di-O-acetyl-2,3-dideoxy-α,β-D-threo-hex-2-enopyranoside 在 咪唑 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 14.0h， 生成 Ethyl 6-O-(tert-butyldimethylsilyl)-2,3-dideoxy-α-D-threo-hex-2-enopyranoside
  参考文献：
  名称：

  Amine-linked diglycosides: Synthesis facilitated by the enhanced reactivity of allylic electrophiles, and glycosidase inhibition assays

  摘要：

  由两个单糖通过桥接氮原子在非异头位置连接而成的双糖衍生物已经合成出来。将其中一个前体单糖耦合组分转化为不饱和衍生物，增强了其在烯丙基位置的亲电性，从而促进了耦合反应。nosyl酰胺和2,3-不饱和-4-醇之间的Mitsunobu耦合得到了反转构型的4-氨基-假双糖，作为单一的区位和对映异构体。胺和2,3-不饱和的4-三氯乙酰亚胺之间的钯催化耦合得到了2-氨基-假双糖作为主要产物，同时还得到了其他次要产物。在假双糖中对C=C双键的衍生化允许形成Man(N4–6)Glc和Man(N4–6)Man双糖苷。发现胺连接的双糖苷显示出较弱的糖苷酶抑制活性。

  DOI：

  10.3762/bjoc.7.128

文献信息

• Synthesis of nitrogen-containing unsaturated carbohydrates via an allyl cyanate-to-isocyanate rearrangement
  作者：Yoshiyasu Ichikawa、Chie Kobayashi、Minoru Isobe

  DOI：10.1039/p19960000377

  日期：——

  A new method for the synthesis of 4-amino-D-hex-2-enopyranosides and 2-amino-D-hex-3-enopyranosides has been developed. The key feature in this method involves construction of the allylamine moiety in the pyranose framework by employing an allyl cyanate-to-isocyanate rearrangement.

  我们开发了一种合成 4-氨基-D-己-2-烯吡喃糖苷和 2-氨基-D-己-3-烯吡喃糖苷的新方法。该方法的主要特点是通过氰酸烯丙酯到异氰酸酯的重排，在吡喃糖框架中构建烯丙基胺分子。
• Synthesis of 2-amino-2-deoxy-D-hexopyranosides from 4-O-trichloroacetimidyl-D-hex-2-enopyranoside by [3,3]-sigmatropic rearrangement
  作者：Kazuyoshi Takeda、Eisuke Kaji、Yaeko Konda、Noriko Sato、Hiroko Nakamura、Noriko Miya、Aya Morizane、Yuko Yanagisawa、Akira Akiyama、Shonosuke Zen、Yoshihiro Harigaya

  DOI：10.1016/s0040-4039(00)60858-4

  日期：1992.11

  2-Amino-2-deoxysugars, D-mannosamine and D-altrosamine derivatives were synthesized together with D-idosamine and D-talosamine ones from a 2-deoxy-2-trichloroacetamido-hex-3-enopyranoside. This key intermediate was prepared by regio- and stereoselective [3,3]-sigmatropic rearrangement of 4-O-trichloroacetimidyl-hex-2-enopyranoside.

  2-氨基-2-脱氧糖，d -mannosamine和d -altrosamine衍生物连同合成d -idosamine和d -talosamine那些从2-脱氧-2- trichloroacetamido -己-3-烯吡喃糖苷。该关键中间体是通过4 - O-三氯乙二酰亚胺-己-2-烯吡喃糖苷的区域和立体选择性[3,3]-σ重排而制备的。
• Palladium-Mediated Cyclization on Carbohydrate Templates. 1. Synthesis of Enantiopure Bicyclic Compounds
  作者：Jean-Flaubert Nguefack、Véronique Bolitt、Denis Sinou

  DOI：10.1021/jo961881o

  日期：1997.3.1

  The bromo unsaturated carbohydrates 30 and 9 were prepared from ethyl 4,6-di-O-acetyl-2,3-dideoxy-D-erythro-hex-2-enopyranoside (1a) and (7) by deacetylation followed by monosilylation with TBDMSCl and then alkylation with BrCH2CBr=CH2. The three analogues 6 and 10 were obtained using the same methodology after inversion at C-4 via a Mitsunobu reaction. The N- and C-analogues 4b and 5 were prepared by palladium alkylation of the carbonate 2d with TsNHCH(2)CBr=CH2 and (CO(2)Me)(2)CHCH2CBr=CH2, respectively. Treatment of the unsaturated carbohydrates 3a and 9 with a catalytic amount of Pd(OAc)(2)/PPh(3) in CH3CN/H2O in the presence of Bu(4)NHSO(4) and NEt(3) afforded the bicyclic compound 14a. The N- and C-analogues 14b and 14c were obtained using the same conditions and starting, respectively, from 4b and 5. On the other hand, treatment of the three derivatives 6 and 10 under these conditions gave the furanic structure 15. In the case of compound 30, performing the reaction in the presence of sodium formate yielded the bicyclic 2-deoxy carbohydrate 17.
• Stereocontrolled palladium(0)-catalyzed preparation of unsaturated azidosugars: an easy access to 2- and 4-aminoglycosides
  作者：Ronaldo N. de Oliveira、Louis Cottier、Denis Sinou、Rajendra M. Srivastava

  DOI：10.1016/j.tet.2005.06.041

  日期：2005.8

  The palladium-catalyzed substitution of alkyl 4,6-di-O-acetyl-alpha-D-erythro-hex-2-eno-pyranosides using NaN3 as the nucleophile gave predominantly the corresponding alkyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-2-enopyranosides in the presence of Pd(PPh3)(4). However, alkyl 6-O-acetyl-4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosi des were obtained as the major products using Pd(PPh3)4 as the catalyst in the presence of dppb as the added ligand. Conversely, alkyl 6-O-(tert-butyidimethylsilyl)-4-0-methoxycarbonyl-2,3-dideoxy-alpha-D-hex-2-enopyranosides gave exclusively alkyl 4-azido-6-O-(tert-butyldimethylsilyi)-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranosides in the presence of Pd-2(dba)(3)/PPh3 as the catalyst and Me3SiN3 as the nucleophile. The bis-hydroxylation followed by hydrogenation of ethyl 4-azido-2,3,4-trideoxy-alpha-D-erythro-hex-2-enopyranoside afforded the corresponding 4-amino-alpha-D-mannopyranoside, when propyl 2-azido-2,3,4-trideoxy-alpha-D-threo-hex-3-enopyranoside gave the 2-amino-alpha-D-altropyranoside under the same conditions. (c) 2005 Elsevier Ltd. All rights reserved.
• VALVERDE, SERAFIN;MARTIN-LOMAS, MANUEL;HERRADON, BARNARDO, J. CARBOHYDR. CHEM., 6,(1987) N 4, 685-690
  作者：VALVERDE, SERAFIN、MARTIN-LOMAS, MANUEL、HERRADON, BARNARDO

  DOI：——

  日期：——