(2R,3R)-2-[(tert-butyldimethylsilanyloxy)methyl]-3-hydroxy-3,6-dihydro-2H-pyran | 273199-64-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃
• 英文名称: (2R,3R)-2-[(tert-butyldimethylsilanyloxy)methyl]-3-hydroxy-3,6-dihydro-2H-pyran
• 英文别名: (2R,3R)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,6-dihydro-2H-pyran-3-ol；6-O-(tert-butyldimethylsilyl)-1,5-anhydro-2,3-dideoxy-D-threo-hex-2-enitol；(2R,3R)-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-3,6-dihydro-2H-pyran-3-ol
• CAS: 273199-64-7
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: DUVZTYKUZSSFEO-GHMZBOCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.32
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R)-2-[(tert-butyldimethylsilanyloxy)methyl]-3-hydroxy-3,6-dihydro-2H-pyran 在 吡啶 、 三乙胺 作用下， 以 乙醚 为溶剂， 反应 26.0h， 生成 (2R,3R)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,6-dihydro-2H-pyran-3-yl (perfluorobenzoyl)oxycarbamate
  参考文献：
  名称：

  Synthesis of the dysiherbaine tetrahydropyran core utilizing improved tethered aminohydroxylation conditions

  摘要：

  A concise stereoselective route to the dysiherbaine tetrahydropyran core was achieved in nine steps and 39% overall yield. Donohoe's improved tethered aminohydroxylation conditions were employed to concurrently install the amino and alcohol groups and construct the tetrahydropyran ring, which features four contiguous cis-stereocenters. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2011.05.106
• 作为产物：
  描述：

  D-三乙酰半乳糖烯 在 咪唑 、 三乙基硅烷 、 indium(III) chloride 、 sodium methylate 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 7.01h， 生成 (2R,3R)-2-[(tert-butyldimethylsilanyloxy)methyl]-3-hydroxy-3,6-dihydro-2H-pyran
  参考文献：
  名称：

  使用束缚的氨基羟基化反应合成dysiherbaine四氢吡喃核。

  摘要：

  以11个步骤完成了dysiherbaine四氢吡喃核心高级中间体的立体控制和可扩展合成，总收率达27％。该合成方法的关键特征是应用Donohoe束缚的氨基羟基化反应来安装氨基二醇并在四氢吡喃环上建立四个连续的顺式立体中心。

  DOI：

  10.1016/j.tetlet.2007.02.016

文献信息

• Synthesis of Novel Tetrahydropyran-Based Dipeptide Isosters by Overman Rearrangement of 2,3-Didehydroglycosides
  作者：Nicole M. A. J. Kriek、Elise van der Hout、Paskal Kelly、Krista E. van Meijgaarden、Annemieke Geluk、Tom H. M. Ottenhoff、Gijs A. van der Marel、Mark Overhand、Jacques H. van Boom、A. Rob P. M. Valentijn、Herman S. Overkleeft

  DOI：10.1002/ejoc.200200710

  日期：2003.7

  Differently functionalized tetrahydropyran-based dipeptide isosters have been efficiently synthesized from 3,4,6-tri-O-acetyl-D-glucal. Analogues of the hsp65 p2−13 epitope of Mycobacterium tuberculosis and Mycobacterium leprae were prepared by replacement of the Ala−Tyr or Glu−Glu moiety in the native dodecapeptide with the prepared dipeptide isosters. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim

  已从 3,4,6-三-O-乙酰基-D-glucal 有效合成了不同功能化的基于四氢吡喃的二肽等排体。结核分枝杆菌和麻风分枝杆菌的 hsp65 p2-13 表位的类似物是通过用制备的二肽等排体替换天然十二肽中的 Ala-Tyr 或 Glu-Glu 部分来制备的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
• Stereochemical Course of Wittig Rearrangements of Dihydropyran Allyl Propargyl Ethers
  作者：Minoru Isobe、Wei-Chung Chang、Pei-Kang Tsou、Chatchawan Ploysuk、Chin-Hui Yu

  DOI：10.1021/acs.joc.5b00678

  日期：2015.6.19

  conformational inversion during the rearrangement, and (4) concerted [2,3]- or [1,2]-Wittig rearrangement. In some cases, a stepwise mechanism that involves the allyl-C–O bond cleavage is shared as the first step by both the [2,3]- and [1,2]-Wittig rearrangements. The stereochemical courses of the rearrangements are compared among the lithiated reactants to determine the reaction pathways. These mechanisms in the

  已经研究了位于2-或4-位的糖衍生的二氢吡喃烯丙基炔丙基醚的[2,3] -Wittig重排，作为通过手性转移延伸4-或2-位碳链的有用手段。这些反应的立体化学过程取决于以下因素：（1）pro - R或pro - S的去质子化-H，（2）锂化的立体异构碳负离子的平衡，（3）重排过程中的构象倒置，以及（4）协同的[2,3]-或[1,2] -Wittig重排。在某些情况下，第一步涉及[2,3]-和[1,2] -Wittig重排，这是涉及烯丙基-C-O键断裂的逐步机理。在锂化的反应物中比较重排的立体化学过程，以确定反应途径。DFT计算进一步支持了多加氧二氢吡喃环系统中的这些机理。
• Ferrier/Aza‐Wacker/Epoxidation/Glycosylation (FAWEG) Sequence to Access 1,2‐ <i>Trans</i> 3‐Amino‐3‐deoxyglycosides
  作者：Anselme Geulin、Yann Bourne‐Branchu、Kawther Ben Ayed、Thomas Lecourt、Antoine Joosten

  DOI：10.1002/chem.202203987

  日期：2023.3.22

  Travelling without moving: A Ferrier rearrangement/aza-Wacker cyclization on commercial glycals allows both a 3,4-cis amination at position three and a motion of the double bound restoring the glycal. Epoxidation/glycosylation of N-Ts 3-amino-3-deoxygalactal provided disaccharide with high diastereoselectivity and yield, thus defining FAWEG (Ferrier/Aza-Wacker/Epoxidation/Glycosylation) as a new sequence

  不移动而移动：商业糖醛上的费里尔重排/aza-Wacker 环化允许在位置 3 进行 3,4-顺式胺化和双键运动恢复糖醛。N -Ts 3-amino-3-deoxygalactal的环氧化/糖基化提供了具有高非对映选择性和产率的二糖，从而将 FAWEG（F errier/ A za- Wacker / E氧化​​/ G糖基化）定义为访问 1,2 的新序列-反式3-氨基-3-脱氧糖苷。
• Conformational Constraint of the Glycerol Moiety of Lysophosphatidylserine Affords Compounds with Receptor Subtype Selectivity
  作者：Sejin Jung、Asuka Inoue、Sho Nakamura、Takayuki Kishi、Akiharu Uwamizu、Misa Sayama、Masaya Ikubo、Yuko Otani、Kuniyuki Kano、Kumiko Makide、Junken Aoki、Tomohiko Ohwada

  DOI：10.1021/acs.jmedchem.5b01925

  日期：2016.4.28

  Lysophosphatidylserine (LysoPS) is an endogenous lipid mediator that specifically activates membrane proteins of the P2Y and its related families of G protein coupled receptors (GPCR), GPR34 (LPS1), P2Y10 (LPS2), and GPR174 (LPS3). Here, in order to increase potency and receptor selectivity, we designed and synthesized LysoPS analogues containing the conformational constraints of the glycerol moiety. These reduced structural flexibility by fixation of the glycerol framework of LysoPS using a 2-hydroxymethyl-3-hydroxytetrahydropyran skeleton, and related structures identified compounds which exhibited high potency and selectivity for activation of GPR34 or P2Y10. Morphing of the structural shape of the 2-hydroxymethyl-3-hydroxytetrahydropyran skeleton into a planar benzene ring enhanced the P2Y10 activation potentcy rather than the GPR34 activation.
• Palladium-Mediated Cyclization on Carbohydrate Templates. 3. Extension of The Cyclization to the Threo Series.
  作者：Karim Bedjeguelal、Laure Joseph、Véronique Bolitt、Denis Sinou

  DOI：10.1080/07328300008544075

  日期：2000.1

  The palladium(0)-catalyzed Heck-type cyclization-beta-alkoxy elimination reaction leading to enantiopure bicyclic compounds in the case of erythro 2,3-unsaturated glycosides has been successfully extended to the three stereoisomer by only changing the aglycon moiety from an ethoxy group to an aryloxy moiety.