(2S,3S,5R,6R)-5-hydroxy-2-methoxy-4-oxo-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3-yl pivalate | 90213-79-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,5R,6R)-5-hydroxy-2-methoxy-4-oxo-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3-yl pivalate
• 英文别名: methyl 2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose；methyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-2-ulose；Methyl-2,6-di-O-pivaloyl-α-D-ribo-hexopyranosid-3-ulose；[(2R,3R,5S,6S)-5-(2,2-dimethylpropanoyloxy)-3-hydroxy-6-methoxy-4-oxooxan-2-yl]methyl 2,2-dimethylpropanoate
• CAS: 90213-79-9
• 化学式: C₁₇H₂₈O₈
• 分子量: 360.405
• InChiKey: LHKVIJJVOFOHCY-WFFHOREQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  25
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  108
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  (2S,3S,5R,6R)-5-hydroxy-2-methoxy-4-oxo-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3-yl pivalate 在 吡啶 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 为溶剂， 反应 17.5h， 生成 methyl 4-deoxy-3,6-di-O-pivaloyl-α-D-glycero-hex-3-endopyranosid-2-ulose
  参考文献：
  名称：

  SYNTHETIC APPROACH TO TETRAHYDROFURAN UNITS AND FIVE-MEMBERED RING LACTONES FUSED TO HEXOPYRANOSIDES ^*

  摘要：

  A stereoselective synthesis of the miharamycin sugar moiety epimer at C-3' was accomplished in high yield starting from an appropriate (Z)-Wittig product, synthesized by Wittig reaction of a 4,6-O-benzylidene protected hexopyranosid-3-ulose with [(ethoxycarbonyl)methylene]triphenylphosphorane followed by iodine promoted isomerisation of the (E)-Wittig product formed. Reduction of the (Z)-isomer obtained in quantitative yield, cyclisation and dihydroxylation with osmium tetroxide, gave the target molecule containing a cis-fused tetrahydrofuran ring in its structure. Synhesis of five-membered rings trans-fused to the hexopyranosidic units succeeded via two different synthetic pathways. Stereoselective Reformatsky reaction of a 2,6-di-O-pivaloyl protected hexopyranosid-3-ulose, followed by cyclisation with dimethylzinc gave a 3,4-trans-fused lactone. The approach using the reaction of 2,3-and 3,4-epoxides with the dianion of phenylselenoacetic acid led to low yield but novel phenylseleno derivatives of trans-fused five-membered rings, namely a phenylselenolactone 2,3-trans-fused to a 4,6-O-benzylidenehexopyranoside and a phenylselenolactenol 3,4-trans-fused to a 6-O-pivaloyl-hexopyranoside.

  DOI：

  10.1081/car-120013489
• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 aluminum oxide 、 pyridinium chlorochromate 作用下， 以 吡啶 、 二氯甲烷 为溶剂， 反应 49.0h， 生成 (2S,3S,5R,6R)-5-hydroxy-2-methoxy-4-oxo-6-(pivaloyloxymethyl)tetrahydro-2H-pyran-3-yl pivalate
  参考文献：
  名称：

  Wittig Reaction: Domino Olefination and Stereoselectivity DFT Study. Synthesis of the Miharamycins’ Bicyclic Sugar Moiety

  摘要：

  2-O-Acyl protected-d-ribo-3-uloses reacted with [(ethoxycarbonyl)methylene]triphenylphosphorane in acetonitrile to afford regio- and stereoselectively 2-(Z)-alkenes in 10-60 min under microwave irradiation. This domino reaction is proposed to proceed via tautomerization of 3-ulose to enol, acyl migration, tautomerization to the 3-O-acyl-2-ulose, and Wittig reaction. Alternatively, in chloroform, regioselective 3-olefination of 2-O-pivaloyl-3-uloses gave (E)-alkenes, key precursors for the miharamycins' bicyclic sugar moiety.

  DOI：

  10.1021/acs.orglett.5b02849

文献信息

• Reactions of N-, S- and O-Nucleophiles with 3,4,6-Tri-O-benzyl-D-glucal Mediated by Triphenylphosphane Hydrobromide versus Those with HY Zeolite
  作者：Amélia P. Rauter、Tânia Almeida、Ana I. Vicente、Verónica Ribeiro、João C. Bordado、João P. Marques、Fernando Ramôa Ribeiro、Maria J. Ferreira、Conceição Oliveira、Michel Guisnet

  DOI：10.1002/ejoc.200500916

  日期：2006.5

  straightforward synthesis of a variety of biomolecules, in moderate to high yield, with the first use of triphenylphosphane hydrobromide for N- and S-glycosylation. An alternative method for C–O and C–S bond formation uses HY zeolite to promote theFerrier rearrangement of 3,4,6-tri-O-benzyl-D-glucal to give exclusively the corresponding 2,3-unsaturated α-O- and α-S-glycosides in moderate yields. (© Wiley-VCH

  通过 1,5-anhydro-3,4,6-tri-O-benzyl-2-deoxy-D-arabino-hex-1-enitol (3,4,6- tri-O-benzyl-D-glucal) 与 N-亲核试剂，使用三苯基膦氢溴酸盐作为二氯甲烷或 THF 中的催化剂。2-脱氧-S-和-O-糖苷也用硫醇、甾醇、类黄酮、醇和糖作为亲核试剂制备，具有α-立体选择性。甾醇、类黄酮、糖和吲哚等空间要求较高的试剂在二氯甲烷中仅产生 α-异头物，而 THF 中的嘌呤核苷作为异头物混合物获得，同时保持 α-立体选择性。这个过程导致了各种生物分子的简单和直接的合成，产量中等至高，首次使用三苯基膦氢溴化物进行 N-和 S-糖基化。C-O 和 C-S 键形成的另一种方法是使用 HY 沸石促进 3,4,6-三-O-苄基-D-glucal 的费里叶重排，专门生成相应的 2,3-不饱和 α-O-和 α-S-糖苷的产量适中。(©
• Visible light photoredox-catalyzed deoxygenation of alcohols
  作者：Daniel Rackl、Viktor Kais、Peter Kreitmeier、Oliver Reiser

  DOI：10.3762/bjoc.10.223

  日期：——

  Carbon–oxygen single bonds are ubiquitous in natural products whereas efficient methods for their reductive defunctionalization are rare. In this work an environmentally benign protocol for the activation of carbon–oxygen single bonds of alcohols towards a reductive bond cleavage under visible light photocatalysis was developed. Alcohols were activated as 3,5-bis(trifluoromethyl)-substituted benzoates and irradiation with blue light in the presence of [Ir(ppy)₂(dtb-bpy)](PF₆) as visible light photocatalyst and Hünig’s base as sacrificial electron donor in an acetonitrile/water mixture generally gave good to excellent yields of the desired defunctionalized compounds. Functional group tolerance is high but the protocol developed is limited to benzylic, α-carbonyl, and α-cyanoalcohols; with other alcohols a slow partial C–F bond reduction in the 3,5-bis(trifluoromethyl)benzoate moiety occurs.

  碳-氧单键在天然产物中普遍存在，而用于其还原脱官能团化的有效方法却很少见。在这项工作中，开发了一种对醇的碳-氧单键进行环境友好的激活，以实现在可见光光催化下的还原键裂解的方法。醇被激活为3,5-双(三氟甲基)取代苯甲酸酯，通过在蓝光照射下，在存在[Ir(ppy)₂(dtb-bpy)](PF₆)作为可见光光催化剂和Hünig's碱作为牺牲电子供体的乙腈/水混合物中，通常可以获得所需的脱官能化化合物的良好至优异产率。对官能团的耐受性很高，但所开发的方法仅限于苄基、α-羰基和α-氰基醇；对于其他醇，3,5-双(三氟甲基)苯甲酸酯中的部分C-F键还原会发生缓慢。
• Deoxygenation at C-4 and Stereospecific Branched-Chain Construction at C-3 of a Methyl Hexopyranuloside. Synthetic Approach to the Amipurimycin Sugar Moiety
  作者：Amélia P. Rauter、Ana C. Fernandes、Stanislas Czernecki、Jean-Marc Valery

  DOI：10.1021/jo952220e

  日期：1996.1.1

  one step in 61% yield. When the system Ph(3)PBr(2)/Ph(3)P was tried, only 8 was formed due to elimination of methanol. The synthesis of 5 was then accomplished by reaction of 8 with methanol in the presence of triphenylphosphine hydrobromide in 37% overall yield. Branched-chain construction was accomplished by Wittig reaction of 5 with [(ethoxycarbonyl)methylene]triphenylphosphorane, followed by osmilation

  描述了从3开始的五步合成，其以47％的总收率得到部分保护的阿米普霉素糖部分14，并且包括在C-4处的脱氧以及支链的区域和立体选择性的构建。通过三种不同的方法可以使C-4为3的脱氧。适当的苯氧基硫代羰基衍生物用氢化三正丁基锡进行自由基还原，由于在C-2上的脱吡咯作用和消除了甲醇，因此以47％的总收率得到了所需的脱氧糖5和副产物6和7。最适当的脱氧程序使用系统Ph（3）P / I（2）/咪唑，可一步一步制得5，收率为61％。尝试使用系统Ph（3）PBr（2）/ Ph（3）P时，由于消除了甲醇，仅形成了8个。然后在三苯膦氢溴酸盐的存在下，通过8与甲醇的反应完成5的合成，总收率为37％。支链的构建是通过5与[（乙氧基羰基）亚甲基]三苯基膦的Wittig反应，然后渗透和用氢化锂铝还原来完成的。14的异丙基亚丙基化制得16的C-6处具有一个游离羟基，用于链延长和氨普霉素的进一步合成。
• HSCN condensation with ulosides: preferred formation of carbohydrate-fused hemiaminals of the 4-hydroxy-1,3-oxazolidine-2-thione type
  作者：Sandrina Silva、Ana Catarina Simão、Arnaud Tatibouët、Patrick Rollin、Amelia Pilar Rauter

  DOI：10.1016/j.tetlet.2007.11.125

  日期：2008.1

  Selected ulofuranosides and ulopyranosides react with thiocyanic acid to give good yields of stable carbohydrate-fused hemiaminal 1,3-oxazolidine-2-thiones. (c) 2007 Elsevier Ltd. All rights reserved.
• A Novel Deoxygenation of Hydroxy Groups Activated by a Vicinal Carbonyl Group <i>via</i> Reaction with Ph₃P/I₂/Imidazole
  作者：Amélia P. Rauter、Ana C. Fernandes、José A. Figueiredo

  DOI：10.1080/07328309808001882

  日期：1998.9.1

  A new procedure for a direct conversion of an alpha-hydroxy sugar ester, lactone or amide into the corresponding alpha-deoxyester , lactone or nitrile using the system Ph-3/I-2 /imidazole is reported. Its efficiency is illustrated by deoxygenation in good yields at position 2 of methyl 3,4:5,6-di-O-isopropylidene-D-gluconate (1), and at positions 5 of 3-O-benzyl-1,2-O-isopropylidene-alpha-D-glucofuranuronamide (3) and 1,2-O-isopropylidene-alpha-D-glucofuranurono-6,3-lactone (5). Reaction with 5,6-O-isopropylidene-L- and -D-gulo-1,4-lactones (7) and (9), respectively, afforded the corresponding alpha,beta-unsaturated lactones in good yields.