(4S,5R)-2,2,5-trimethyl-1,3-dioxolane-4-carbaldehyde | 99603-55-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4S,5R)-2,2,5-trimethyl-1,3-dioxolane-4-carbaldehyde
• 英文别名: (4S)-trans-2,2,5-trimethyl-1,3-dioxolane-4-carboxaldehyde
• CAS: 99603-55-1
• 化学式: C₇H₁₂O₃
• 分子量: 144.17
• InChiKey: BWFCUWGVXQIDQS-PHDIDXHHSA-N

物化性质

• 沸点：
  179.1±25.0 °C(Predicted)
• 密度：
  1.061±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.4
• 重原子数：
  10
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (4S,5R)-2,2,5-trimethyl-1,3-dioxolane-4-carbaldehyde 在 盐酸 、 正丁基锂 、 sodium cyanoborohydride 、 对甲苯磺酸 、 溶剂黄146 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 乙腈 为溶剂， 反应 35.5h， 生成 ethyl (2R,3R,4S,5R)-3-benzyloxy-4,5-isopropylidenedioxy-2-[N-methyl-M-(diphenylmethyl)amino]hexanoate
  参考文献：
  名称：

  Amino acid based diastereoselective synthesis of fucosamines

  摘要：

  Enantiomerically pure (+)-D-fucosamine 1, (+)-N-methyl-D-fucosamine 2 and (+)-3-O-methyl-D-fucosamine 3 (elsaminose) have been synthesised from known building blocks derived from natural amino acids. Direct and diastereoselective construction of the key intermediate 8 was accomplished by a highly syn,anti-selective aldol reaction between lithiated Schollkopf's bis-lactim ether 7 and the 1,3-dioxolane-4-carboxaldehyde 5. Elaboration of the common intermediate required optional methylation, selective hydrolysis of the bis-lactim ether in the presence of an isopropylidene ketal, lactonization and partial reduction of the carboxylic group. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(02)00376-2
• 作为产物：
  描述：

  2,3:4,5-di-O-isopropylidene-D-arabinose diethyldithioacetal 在 镍 lead(IV) acetate 、 溶剂黄146 作用下， 以 乙醇 、 乙酸乙酯 为溶剂， 反应 3.25h， 生成 (4S,5R)-2,2,5-trimethyl-1,3-dioxolane-4-carbaldehyde
  参考文献：
  名称：

  Eine einfache Synthese aller vier stereoisomeren 2,2,5-Trimethyl-1,3-dioxolan-4-carbaldehyde

  摘要：

  A simple and efficient procedure for the syntheses of all four stereoisomers of the 2,2,5-trimethyl-1,3-dioxolane-4-carbaldehydes 1a-1d has been developed. Starting with readily available aldopentose diethyl dithioacetals 2, 6, 10 and 14, the title compounds were obtained by a selective protecting group strategy and subsequent Raney-nickel reduction, followed by lead tetraacetate cleavage. This procedure allows an application on a multigram scale.

  DOI：

  10.1007/bf01277638

文献信息

• Histidine-Catalyzed Asymmetric Aldol Addition of Enolizable Aldehydes: Insights into its Mechanism
  作者：Ulf Scheffler、Rainer Mahrwald

  DOI：10.1021/jo202558f

  日期：2012.3.2

  Extensive studies of asymmetric cross-aldol addition between enolizable aldehydes are described and provide a deeper insight into histidine-catalyzed aldol additions. In particular, aspects of enantio- as well as diastereoselectivity of these reactions are discussed. Rules and predictions of configurative outcome are explained by using different transition-state models. These discussions are confirmed

  描述了可烯化醛之间不对称交叉羟醛加成的广泛研究，并为组氨酸催化的羟醛加成提供了更深入的了解。特别是，讨论了这些反应的对映选择性和非对映选择性。通过使用不同的过渡状态模型来解释配置结果的规则和预测。这些讨论已通过大量的计算得到证实。
• On the selectivity of oxynitrilases towards α-oxygenated aldehydes
  作者：Paola Bianchi、Gabriella Roda、Sergio Riva、Bruno Danieli、Antonina Zabelinskaja-Mackova、Herfried Griengl

  DOI：10.1016/s0040-4020(01)00054-0

  日期：2001.3

  Different α-alkoxy and α,β-di-alkoxy substituted aldehydes have been submitted to the catalytic action of the oxynitrilases from almond (PaHNL) or from Hevea brasiliensis (HbHNL), in order to explore the possibility of using these enzymes for the preparation of complex cyanohydrins. The selectivity of both enzymes towards these compounds was found to be largely dependent on the substitutents, being

  不同α -烷氧基和α，β二-烷氧基取代的醛已经被提交到醇腈的从杏仁催化作用（PaHNL）或者从巴西橡胶树（HbHNL），为了探索使用这些酶制剂的可能性复杂的氰醇。发现两种酶对这些化合物的选择性在很大程度上取决于取代基，因为醛带有在空间上更需要的苯基取代基的醛较低。违背化学添加HCN，它总是与用于形成的轻微偏爱发生的反非对映体，所述酶cyanuration存在与面部偏好，硅或再根据所使用的生物催化剂，得到氰醇的混合物，取决于起始的对映异构醛，该混合物可以富含顺式非对映异构体。
• Synthetic studies towards the total synthesis of olivin: Synthesis of a fully functionalized alkyne appropriate for the benzannulation reaction
  作者：Adam M. Gilbert、Ross Miller、William D. Wulff

  DOI：10.1016/s0040-4020(98)01206-x

  日期：1999.2

  B-ring of olivin. This alkyne incorporates four of the five asymmetric centers in the aglycone of olivin. The synthesis of this alkyne begins with the exclusively syn selective Mukaiyama aldol reaction of 2-trimethylsiloxyfuran with the 2S,3R-dihydroxybutanal protected as its acetonide. Conjugate addition of a vinyl cuprate to the butenolide obtained from this reaction gives a single stereoisomer of an

  已经开发出合成橄榄酯的合成策略，其特征在于在包含无环碳水化合物侧链的分子的三环核的组装中费歇尔卡宾配合物的苯并环反应和已区分的苯酚功能。在这项工作中，开发了一种关键炔烃的合成方法，该方法可用于构建寡聚烯丙基B环的苯环化反应中。该炔烃在橄榄素的糖苷配基中结合了五个不对称中心中的四个。该炔烃的合成始于2-三甲基甲硅烷氧基呋喃与被保护为其丙酮化物的2S，3R-二羟基丁醛的完全同位选择性的Mukaiyama aldol反应。在由该反应获得的丁烯内酯中共轭添加铜酸铜乙烯酯，得到中间体的单一立体异构体，该中间体具有无环碳水化合物侧链的所有手性中心。炔烃中的最终碳是通过Corey-Fuchs反应引入的，该反应用于安装炔烃功能。炔烃的合成分15步（总收率6％）完成，可提供克量的材料。关键苯并环化步骤的初步评估是使用炔烃进行的图45和卡宾配合物44证明了使用芳基费歇尔卡宾配合物与含有炔烃合成所需的官能团的复杂炔烃反应的合成策略的可行性。
• Synthesis of amino sugars through a highly diastereoselective dipolar cycloaddition. Enantioselective synthesis of the carbohydrate segment of Sch 38516
  作者：Zhongmin Xu、Charles W Johannes、Daniel S La、Gloria E Hofilena、Amir H Hoveyda

  DOI：10.1016/s0040-4020(97)01023-5

  日期：1997.12

  A concise and stereoselective route for the synthesis of the carbohydrate moiety of the antifungal agent Sch 38516 is described. The synthesis scheme includes a dipolar cycloaddition, which is rendered diastereoselective through the use of a readily available and easily removable chiral auxiliary.

  描述了用于合成抗真菌剂Sch 38516的碳水化合物部分的简明和立体选择性的途径。该合成方案包括偶极环加成，其通过使用容易获得且易于除去的手性助剂而成为非对映选择性的。
• Synthetic Studies toward the Construction of the <i>cis</i>-Decalin Portion of Superstolides A and B. Application of a Sequential Double Michael Reaction and an Anionic Oxy-Cope Rearrangement
  作者：Zhengmao Hua、Wensheng Yu、Mei Su、Zhendong Jin

  DOI：10.1021/ol050339w

  日期：2005.5.1

  A highly convergent strategy for the asymmetric synthesis of the cis-decalin portion of the antitumor macrolide superstolide A was developed. The key reactions in our approach involve a sequential double Michael reaction and an anionic oxy-Cope rearrangement.

  针对抗肿瘤大环内酯类超环氧化物A的顺式十氢化萘部分的不对称合成，提出了一种高度收敛的策略。我们方法中的关键反应包括连续的双迈克尔反应和阴离子氧基-Cope重排。