2,2-dimethyl-5-vinyl-1,3-dioxan-5-ol | 933791-84-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-dimethyl-5-vinyl-1,3-dioxan-5-ol
• 英文别名: 5-ethenyl-2,2-dimethyl-1,3-dioxan-5-ol
• CAS: 933791-84-5
• 化学式: C₈H₁₄O₃
• mdl: MFCD12922679
• 分子量: 158.197
• InChiKey: GQXRFZKRWQOCST-UHFFFAOYSA-N

物化性质

• 沸点：
  247.0±40.0 °C(Predicted)
• 密度：
  1.104±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  38.7
• 氢给体数：
  1
• 氢受体数：
  3

安全信息

• 危险等级：
  IRRITANT

反应信息

• 作为反应物：
  描述：

  2,2-dimethyl-5-vinyl-1,3-dioxan-5-ol 在 盐酸 、 4-二甲氨基吡啶 、 三乙胺 、 对甲苯磺酰氯 、 copper dichloride 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 20.0h， 生成
  参考文献：
  名称：

  通过对2-取代的甘油进行去对称化苯甲酰化来对叔醇进行对映选择性合成。

  摘要：

  DOI：

  10.1002/anie.200604977
• 作为产物：
  描述：

  2,2-二甲氧基丙烷 在 乙酸酐 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 32.0h， 生成 2,2-dimethyl-5-vinyl-1,3-dioxan-5-ol
  参考文献：
  名称：

  番茄酸和立体异构体的全合成（第 1 部分）：外消旋烯酰胺的双重不对称氢化

  摘要：

  据报道，外消旋烯酰胺的设计、合成和双不对称氢化可用于番茄酸及其异构体的立体发散合成。氢化结果（产率，ee）用于识别匹配和不匹配的产物，该信息对于阐明反应机理非常重要。还提出，如果反应机理已知，则无需通过匹配/不匹配分析进行光谱分析即可鉴定产物的结构。

  DOI：

  10.1016/j.tet.2023.133622

文献信息

• Catalytic Radical–Polar Crossover Reactions of Allylic Alcohols
  作者：Eric E. Touney、Nicholas J. Foy、Sergey V. Pronin

  DOI：10.1021/jacs.8b12075

  日期：2018.12.12

  Radical-polar crossover hydrofunctionalizations of tertiary allylic alcohols are described. Depending on the structure of the catalyst, corresponding epoxides or semipinacol rearrangement products are selectively obtained in good yields. Experimental evidence points to the participation of alkylcobalt complexes as electrophilic intermediates.

  描述了叔烯丙醇的自由基极性交叉氢官能化。取决于催化剂的结构，相应的环氧化物或半频哪醇重排产物以良好的产率选择性地获得。实验证据表明烷基钴配合物作为亲电子中间体的参与。
• [EN] PROCESS FOR PREPARING AN ANTI-HYPERCHOLESTEROLEMIC COMPOUND<br/>[FR] PROCÉDÉ DE PRÉPARATION D'UN COMPOSÉ ANTI-HYPERCHOLESTÉROLÉMIANT
  申请人：MERCK & CO INC

  公开号：WO2009054887A1

  公开（公告）日：2009-04-30

  The present invention relates to a process for preparing inhibitors of cholesterol absorption of Formula II: II and the pharmaceutically acceptable salts and esters thereof, employing a metal-catalyzed dynamic kinetic resolution (DKR) asymmetric transfer hydrogenation (ATH) reaction of racemic acyclic ß-ketoamide bearing a-substituted aliphatic side chain (Intermediate A) and subsequent cyclization of the resulting b-hydroxyamide product (Intermediate B), followed by a synthesis involving two consecutive cross-coupling reactions.

  本发明涉及一种制备胆固醇吸收抑制剂的方法，该方法涉及使用金属催化的动态动力学分辨（DKR）不对称转移氢化（ATH）反应，对具有α-取代脂肪侧链的无光学活性β-酮酰胺（中间体A）进行环化，得到b-羟基酰胺产物（中间体B），然后通过两个连续的交叉偶联反应进行合成。
• Asymmetric total synthesis of (+)-(2<i>R</i>,4′<i>R</i>,8′<i>R</i>)-α-tocopherol enabled by enzymatic desymmetrization
  作者：Haidi Yang、Jinyao Liu、Pan Hu、Liang Gao、Zedu Huang、Fener Chen

  DOI：10.1039/d2ob00384h

  日期：——

  configuration in 81% yield and 96.7% ee, to the best of our knowledge, leading to the most efficient enzymatic desymmetric synthesis of the chiral chroman skeleton of vitamin E members reported to date. Coupled with the modified preparation of the phytol-derived side chain, the chemoenzymatic total synthesis of 1 was completed in 15 longest linear steps with 3.1% overall yield.

  手性二醇 ( S ) -14是 (+)-(2 R ,4' R ,8' R )-α-生育酚 ( 1 ) 的常见合成中间体，一种新的高度立体选择性合成方法分七个步骤完成总产率为 13.8%。该开发路线的特点是脂肪酶催化的前手性二酯39a的不对称水解，其通过具有挑战性的 Heck 偶联制备成手性含季碳单酯 ( R ) -37a据我们所知，在 81% 的产率和 96.7% 的正确配置下，导致迄今为止报道的维生素 E 成员的手性色满骨架的最有效的酶促不对称合成。再加上对植醇衍生侧链的修饰制备，1的化学酶促全合成在 15 个最长的线性步骤中完成，总产率为 3.1%。
• Synthesis of Carbohydrates in Mineral-Guided Prebiotic Cycles
  作者：Hyo-Joong Kim、Alonso Ricardo、Heshan I. Illangkoon、Myong Jung Kim、Matthew A. Carrigan、Fabianne Frye、Steven A. Benner

  DOI：10.1021/ja201769f

  日期：2011.6.22

  One present obstacle to the "RNA-first" model for the origin of life is an inability to generate reasonable "hands off" scenarios for the formation of carbohydrates under conditions where they might have survived for reasonable times once formed. Such scenarios would be especially compelling if they deliver pent(ul)oses, five-carbon sugars found in terran genetics, and exclude other carbohydrates (e.g., aldotetroses) that may also be able to function in genetic systems. Here, we provide detailed chemical analyses of carbohydrate premetabolisin, showing how borate, molybdate, and calcium minerals guide the formation of tetroses (C(4)H(8)O(4)), heptoses (C(7)H(14),O(7)), and pentoses (C(5)H(10)O(5)), including the ribose found in RNA, in "hands off" experiments, starting with formaldehyde and glycoaldehyde. These results show that pent(ul)oses would almost certainly have formed as stable borate complexes on the surface of an early Earth beneath a humid CO(2) atmosphere suffering electrical discharge. While aldotetroses form extremely stable complexes with borate, they are not accessible by pathways plausible under the most likely early Earth scenarios. The stabilization by borate is not, however, absolute. Over longer times, material is expected to have passed from borate-bound pent(ul)oses to a branched heptulose, which is susceptible to Cannizzaro reduction to give dead end products. We show how this fate might be avoided using molybdate-catalyzed rearrangement of a branched pentose that is central to borate-moderated cycles that fix carbon from formaldehyde. Our emerging understanding of the nature of the early Earth, including the presence of hydrated rocks undergoing subduction to form felsic magmas in the early Hadean eon, may have made borate and molydate species available to prebiotic chemistry, despite the overall "reduced" state of the planet.