4-O-benzyl-2,3-O-isopropylidene-aldehydo-D-erythrose | 81801-08-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-O-benzyl-2,3-O-isopropylidene-aldehydo-D-erythrose
• 英文别名: 4-O-benzyl-2,3-O-isopropylidene-D-erythrose；4-O-benzyl-2,3-O-isopropylidene-L-threose；(4R,5R)-2,2-dimethyl-5-(phenylmethoxymethyl)-1,3-dioxolane-4-carbaldehyde
• CAS: 81801-08-3
• 化学式: C₁₄H₁₈O₄
• 分子量: 250.295
• InChiKey: BCWIHZPGMUVRNG-QWHCGFSZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  4-O-benzyl-2,3-O-isopropylidene-aldehydo-D-erythrose 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 sodium hydroxide 、 lithium aluminium tetrahydride 、 三氯化铝 、 L-(+)-酒石酸二异丙酯 、 sodium hydride 作用下， 以 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 67.0h， 生成 (1R,2R)-1-((4S,5R)-5-((benzyloxy)methyl)-2,2-dimethyl-1,3-dioxolan-4-yl)propane-1,2,3-triol
  参考文献：
  名称：

  Synthesis of saccharides and related polyhydroxylated natural products. 1. Simple alditols

  摘要：

  DOI：

  10.1021/jo00346a051
• 作为产物：
  描述：

  2,3,5,6-di-isopropyIidene-1,4-dihydroxy-D-mannitol 在 sodium periodate 、 四丁基碘化铵 、 高碘酸 、 silver(l) oxide 作用下， 以 甲醇 、 水 、 乙酸乙酯 为溶剂， 反应 24.0h， 生成 4-O-benzyl-2,3-O-isopropylidene-aldehydo-D-erythrose
  参考文献：
  名称：

  Enantioselective Synthesis of Ethyl 4,5,7,8,9-Penta-O-acetyl-2,6-anhydro- 3-deoxy-D-erythro-L-gluca-nononate: a 2-Monodeoxygenated Derivative of `2-Keto-3-deoxy-D-glycero-D-galacto-nononic Acid'

  摘要：

  A study aimed at developing an enantioselective synthesis of the title compound 23, a 2-monodeoxy analogue of;he naturally occurring (+)-2-keto-3-deoxy-D-glycero-D-galacto-2-nononic acid (KDN),is reported. From D-mannose as starting material, the chiral 1,3-diene 10, activated by a silyloxy substituent at C(2), was prepared in six steps (Scheme I). However, the intermediates were often contaminated with varying amounts of by-products arising from overoxidation during cleavage with periodic acid. An alternative route starting from the inexpensive and readily available D-isoascorbic acid (12), though a little longer than the first, satisfactorily circumvented the purification problem and led to the desired dienes 17 in good yields (scheme2). The [Co-II(S.S)-(+)-salen]-catalyzed hetero-Diels-Alder reactions of the aforementioned dienes with ethyl glyoxylate proceeded smoothly at room temperature, giving the dihydropyrano adducts 18 in moderate yields (Scheme 3). Dihydroxylation of 18a followed by reduction of the keto function gave the desired 4,5-trans dihydroxy moiety of the KDN framework (Scheme 4, see 21). The spectroscopic data of the penta-O-acetylated 2-deoxy-KDN ethyl ester 23 were consistent with those reported for the corresponding methyl ester derived from natural KDN.

  DOI：

  10.1002/(sici)1522-2675(20000510)83:5<943::aid-hlca943>3.0.co;2-h

文献信息

• Chromium-Mediated Stereoselective Synthesis of Carbohydrate-Derived (<i>E</i>)-α,β-Unsaturated Esters or Amides
  作者：Humberto Rodríguez-Solla、Carmen Concellón、Elena G. Blanco、Juan Ignacio Sarmiento、Pamela Díaz、Raquel G. Soengas

  DOI：10.1021/jo200548g

  日期：2011.7.1

  A chromium-mediated novel synthesis of carbohydrate-derived di- and trisubstituted (E)-α,β-unsaturated esters or amides from a range of dichloroesters or amides and a variety of sugar aldehydes is reported. The process took place with total stereoselectivity and in high yields. A mechanism based on a sequential chromium-promoted aldol-type reaction and a completely stereoselective β-elimination reaction

  据报道，铬介导的由碳水化合物衍生的二和三取代的（E）-α，β-不饱和酯或酰胺由一系列二氯酯或酰胺和各种糖醛合成。该过程以总的立体选择性和高收率进行。提出了一种基于顺序铬促进的醛醇型反应和完全立体选择性β-消除反应的机理来解释这些结果。
• Chemistry of Pyruvate Enolates:<i>anti</i>-Selective Direct Aldol Reactions of Pyruvate Ester with Sugar Aldehydes Promoted by a Dinuclear Zinc Catalyst
  作者：Marta A. Molenda、Sebastian Baś、Osama El-Sepelgy、Matylda Stefaniak、Jacek Mlynarski

  DOI：10.1002/adsc.201500169

  日期：2015.6.15

  A chiral dinuclear zinc complex can effectively catalyse the direct aldol reactions of pyruvic acid ester with various chiral sugar aldehydes, thus functionally mimicking the pyruvate‐dependent type II aldolases. Application of sterically hindered aryl esters allows for the elusive aldol reaction of the pyruvate donor with controlled anti‐selectivity en route to the short and efficient synthesis of

  手性双核锌络合物可以有效催化丙酮酸酯与各种手性糖醛的直接醛醇缩合反应，从而在功能上模仿丙酮酸依赖性的II型醛缩酶。的空间位阻的芳基酯的应用允许与控制的丙酮酸供体的难以捉摸的醛醇缩合反应的抗-选择性途中到的3-脱氧-2- ulosonic氨基酸的短和高效合成。丙酮酸酯在模仿自然界中使用的合成原理时，被用作丙酮酸丙酮醇（PEP）的化学等同物。提出的仿生方法使用烯醇形成来高效和灵活地形成各种C 6 -C 9ulosonic酸。3-脱氧的具体地，有效和简洁的合成d -赤-己-2-糖酸（KDG，总产率50％），3-脱氧d -核糖-庚-2-糖酸（DRH，整体的53％收率）和3-脱氧d -甘油基- d -距骨-壬-2-糖酸（4-外延-KDN，总产率78％）中有描述。丙酮酸酯的这种直接有效应用不需要额外的脱掩蔽步骤，因此超越了以前使用掩蔽的丙酮酸合成子（例如2-乙酰基噻唑和丙酮醛二甲基乙缩醛）的方法。
• Diastereoselective Synthesis of Piperidine Imino Sugars Using Aldol Additions of Metalated Bislactim Ethers to Threose and Erythrose Acetonides
  作者：María Ruiz、Tania M. Ruanova、Olga Blanco、Fátima Núñez、Cristina Pato、Vicente Ojea

  DOI：10.1021/jo702601z

  日期：2008.3.1

  anti-selectivity for the mismatched ones may originate from (1) the intervention of solvated aggregates of tin(II) azaenolate and lithium chloride as the reactive species and (2) favored chair-like transition structures with a Cornforth-like conformation for the aldehyde moiety. DFT calculations indicate that aldol additions to erythrose acetonides proceed by an initial deprotonation, followed by coordination

  描述了从手性甘氨酸当量和4-碳构件合成1-脱氧-天冬酰胺的一般策略。非对映选择性醛醇缩合的金属化双lactimin醚添加到匹配和不匹配的赤藓糖或苏糖酸丙酮化物和分子内氮-烷基化（通过还原胺化或亲核取代）被用作关键步骤。研究了赤藓糖或苏糖醛丙酮化物中氮杂烯酸酯的金属抗衡离子和γ-烷氧基保护基的性质和醛醇加成的收率和不对称诱导的关系。借助密度泛函理论（DFT）计算已经合理化了氮杂锡（II）锡与羟醛加成的立体化学结果。按照理论计算与模型甘油丙酮化，高反式，顺式，反-selectivitity的配对和适度低反式，反，反错配的选择性可能源于（1）干预作为活性物质的氮杂锡（II）和氯化锂（II）的溶剂化团聚体；（2）醛基具有类似于Cornforth构象的椅子样过渡结构。DFT计算表明，向赤藓糖醇丙酮中添加羟醛的过程是先进行去质子化，然后将烷氧基衍生物与氮杂锡（II）配位，并通过周环过渡结构最终重组中间
• A Concise Organocatalytic Synthesis of 3-Deoxy-2-ulosonic Acids through<i>Cinchona</i>-Alkaloid-Promoted Aldol Reactions of Pyruvate
  作者：Marta A. Molenda、Sebastian Baś、Jacek Mlynarski

  DOI：10.1002/ejoc.201600784

  日期：2016.9

  concise syntheses of diverse six-, seven-, eight-, and nine-carbon ulosonic acid esters are described, by using a biomimetic three-carbon chain elongation of various sugar aldehydes. Consequently, short and practical syntheses of several ulosonic acids, including three important naturally occurring sugars – 3-deoxy-d-erythro-hex-2-ulosonic acid (KDG), 3-deoxy-d-manno-oct-2-ulosonic acid (KDO), and

  由纯有机催化剂介导的丙酮酸酯与手性醛的直接交叉羟醛反应被描述为合成磺酸的关键步骤。含有叔胺基团的金鸡纳生物碱有效地促进了位阻丙酮酸酯与各种糖醛的直接羟醛反应。丙酮酸酯可直接作为PEP（磷酸烯醇式丙酮酸）的化学等价物，模仿自然界使用的合成原理。手性醛与手性催化剂的适当组合允许根据需要灵活地制备反构型或顺构型羟醛。因此，通过使用各种糖醛的仿生三碳链延长，描述了多种六碳、七碳、八碳和九碳磺酸酯的简明合成。最后，
• Highly stereocontrolled access to a tetrahydroxy long chain base using anti-selective additions
  作者：Makoto Shimizu、Manabu Kawamoto、Yasuki Niwa

  DOI：10.1039/a902386k

  日期：——

  Complete diastereostereoselection was attained for the addition of acetylide and benzyloxymethyl anions to a chiral aldehyde and an imine derived from meso-tartaric acid, leading to a facile synthesis of (2S,3S,4R,5R,6Z)-2-amino-1,3,4,5-tetrahydroxyoctadecene as its pentaacetyl derivative in enantiomerically pure form.

  对乙炔和苄氧基甲基阴离子与来自酒石酸的手性醛和亚胺的加成实现了完全的非对映体选择性，从而方便地合成了其五乙酰衍生物—(2S,3S,4R,5R,6Z)-2-氨基-1,3,4,5-四羟基十八烯，以对映体纯净的形式。