3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-gluco-2-heptulopyranose | 140926-87-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-gluco-2-heptulopyranose
• 英文别名: (2R,3R,4S,5R,6R)-2-(dimethoxyphosphorylmethyl)-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-2-ol
• CAS: 140926-87-0
• 化学式: C₃₇H₄₃O₉P
• 分子量: 662.717
• InChiKey: IWDFDXKOAWXJTN-MANRWTMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  47
• 可旋转键数：
  17
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  102
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-gluco-2-heptulopyranose 在 18-冠醚-6 sodium tetrahydroborate 、 三丁基膦 、 dimethyl sulfide borane 、 L-Selectride 、 potassium carbonate 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 三氟乙酸酐 、 1,1'-azodicarbonyl-dipiperidine 作用下， 以 四氢呋喃 、 二氯甲烷 、 甲苯 为溶剂， 反应 26.25h， 生成 (2S,3R,4S,5R,6R)-2-[2-[(4-methoxyphenyl)methyl]phenoxy]-3,4,5-tris(phenylmethoxy)-6-(phenylmethoxymethyl)cyclohexan-1-one
  参考文献：
  名称：

  [EN] FAMILY OF ARYL, HETEROARYL, O-ARYL AND O-HETEROARYL CARBASUGARS
  [FR] FAMILLE DE CARBASUCRES ARYLIQUES, HÉTÉROARYLIQUES, O-ARYLIQUES ET O-HÉTÉROARYLIQUES

  摘要：

  本发明涉及以下通式（I）的化合物，以及其制备方法、包含该化合物的医药和化妆品组合物及其用途，特别是作为钠依赖性葡萄糖共转运体抑制剂，例如SGLT1、SGLT2和SGLT3，特别是在治疗或预防糖尿病，尤其是II型糖尿病、糖尿病相关并发症（如下肢关节炎、心肌梗死、肾功能不全、神经病变或失明）、高血糖、高胰岛素血症、肥胖、高甘油三酯血症、X综合征和动脉硬化中的应用，以及作为抗癌、抗感染、抗病毒、抗血栓或抗炎药物的用途，或用于美白、漂白、脱色素皮肤、去除皮肤瑕疵，特别是老年斑和雀斑，或预防皮肤色素沉着。

  公开号：

  WO2012160218A1
• 作为产物：
  描述：

  2,3,4,6-四苄基-D-吡喃葡萄糖 在 正丁基锂 、 二甲基亚砜 作用下， 以 乙酸酐 为溶剂， 生成 3,4,5,7-tetra-O-benzyl-1-deoxy-1-dimethoxyphosphoryl-α-D-gluco-2-heptulopyranose
  参考文献：
  名称：

  轻松合成共轭外糖

  摘要：

  探索了两种用于合成各种缀合的外糖的有效方法：（i）通过亲核加糖内酯并随后进行脱水，以及（ii）C-糖苷的硒化并随后去除亚硒氧化物。这些反应以立体选择性方式发生，以仅或主要给出外糖的（Z）-异构体。

  DOI：

  10.1016/s0040-4039(01)01427-7

文献信息

• Stereochemistry in the Synthesis and Reaction of <i>e</i><i>xo</i>-Glycals
  作者：Wen-Bin Yang、Yu-Ying Yang、Yu-Feng Gu、Shwu-Huey Wang、Che-Chien Chang、Chun-Hung Lin

  DOI：10.1021/jo0255227

  日期：2002.5.1

  Two general methods are explored for the stereoselective synthesis of exo-glycals. One method utilizes a nucleophilic addition of fully protected sugar lactones of gluco-, galacto-, and manno-types, followed by the subsequent dehydration, to give the desired exo-glycals with (Z)-configuration. The other method proceeds with selenylation of C-glycosides in a stereoselective manner. The subsequent selenoxide

  探索了两种一般方法来立体选择性合成外糖。一种方法利用亲核加成葡萄糖，半乳糖和甘露糖型的完全保护的糖内酯，随后进行脱水，以得到具有（Z）构型的期望的外糖。另一种方法以立体选择性方式进行C-糖苷的硒化。随后的亚硒酸盐消除也提供了（Z）-外糖。制备的葡萄糖型或甘露型的外糖共轭酯与烯丙醇反应，仅得到α-异头物。
• Novel UDP-Glycal Derivatives as Transition State Analogue Inhibitors of UDP-GlcNAc 2-Epimerase
  作者：Florian Stolz、Martin Reiner、Astrid Blume、Werner Reutter、Richard R. Schmidt

  DOI：10.1021/jo0353029

  日期：2004.2.1

  the first step in the biosynthesis of sialic acids, is catalyzed by UDP-GlcNAc 2-epimerase. In this paper we report the synthesis of transition state based inhibitors of this enzyme. To mimic the assumed first transition state of this reaction (TS 1), we designed and synthesized the novel UDP-exo-glycal derivatives 1−4. We also report herein the synthesis of 5 and 6, the first C-glycosidic derivatives

  UDP-GlcNAc 2-epimerase催化将唾液酸生物合成过程中的第一步从UDP-GlcNAc到ManNAc的“表位化”。在本文中，我们报告了该酶基于过渡态抑制剂的合成。为了模拟该反应的假定的第一过渡态（TS 1），我们设计并合成了新型UDP-外糖基衍生物1-4。我们在此还报告了5和6的合成，2-乙酰氨基葡糖的第一个C-糖苷衍生物以及酮苷7和8的合成，它们分别被设计为双底物类似物和双产物类似物，以模拟通过假定的第二过渡态TS 2进行反应的第二步。
• Stereoselective synthesis of C-glycosylphosphonates from their ketols. Reconsideration of an abandoned route
  作者：Alessandro Dondoni、Alberto Marra、Claudia Pasti

  DOI：10.1016/s0957-4166(99)00477-2

  日期：2000.1

  Isosteric phosphonate analogues of glycosyl 1-phosphates have been obtained by addition of LiCH2P(O)(OMe)(2) to glyconolactones followed by Et3SiH-TMSOTf reductive dehydroxylation of the resultant ketols. The compounds prepared include four beta-linked pyranose derivatives (D-galacto, 2-azido-2-deoxy-D-galacto, D-gluco, D-manno) and one beta-linked furanose derivative (D-manno). In the latter case the ketol was activated as its 2-acetate. In agreement with an observation in another laboratory, the dehydroxylation of a model ketol phosphonate failed with the use of Et3SiH-BF3. Et2O. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Synthesis of valiolamine and its N-substituted derivatives AO-128, validoxylamine G, and validamycin G via branched-chain inosose derivatives
  作者：Hiroshi Fukase、Satoshi Horii

  DOI：10.1021/jo00039a026

  日期：1992.6

  Novel synthetic routes to valiolamine (1a) and N-substituted valiolamine derivatives via branched-chain inosose derivatives are described. (1S)-(1(OH),2,4/1,3)-2,3,4-Tri-O-benzyl-1-C-[(benzyloxy)methyl]-5-oxo-1,2,3,4-cyclohexanetetrol (3), a branched-chain inosose derivative prepared from D-glucose, 2 has been converted into 1a via the ketoxime 7 followed by hydrogenation. N-Substituted valiolamine derivatives having strong alpha-D-glucosidase inhibitory activity have been synthesized by the direct reductive amination of the branched-chain inosose derivative 3 with an appropriate amino compound to construct the N-substituent moiety, followed by removal of the O-benzyl protecting group. The stereoselective preparation of two representative derivatives, N-[2-hydroxy-1-(hydroxymethyl)ethyl]valiolamine (2a, AO-128)3 and N-[1R,2R)-2-hydroxyclohexyl]valiolamine (2b)3 is described. Application of branched-chain inosose derivatives 3 and 23 to the total synthesis of natural N-substituted valiolamine derivatives validoxylamine G (5a) and validamycin G (6a) is also described.