(2R,4S,5R)-5-hydroxy-2-phenyl-4-vinyl-1,3-dioxane | 133782-90-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: (2R,4S,5R)-5-hydroxy-2-phenyl-4-vinyl-1,3-dioxane
• 英文别名: (2R,4S,5R)-2-phenyl-4-vinyl-m-dioxan-5-ol；2-phenyl-4-vinyl-1,3-dioxan-5-ol；(2R,4S,5R)-4-ethenyl-2-phenyl-1,3-dioxan-5-ol
• CAS: 133782-90-8
• 化学式: C₁₂H₁₄O₃
• 分子量: 206.241
• InChiKey: MFZPVVWDHKXMOL-GRYCIOLGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 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,4S,5R)-5-hydroxy-2-phenyl-4-vinyl-1,3-dioxane 在 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 双氧水 作用下， 生成 (2R,4S,5R)-5-hydroxy-2-phenyl-m-dioxane-4-ethanol
  参考文献：
  名称：

  Stereochemical Models for the Enantiocontrolled Construction of Fully Functionalized C Rings via Intramolecular Aldolization in Advanced Precursors to Paclitaxel

  摘要：

  Six transition-state models for intramolecular aldol C-ring annulation in suitably substituted bicyclo-[6.2.1]undecanones have been defined. The first consideration is the inherent conformational flexibility of the nine-membered ketonic ring which does not limit effective deprotonation to a single C-8 epimer. When the oxygen substituents at C-4 and C-5 are not covalently linked, the configuration at C-5 defines the stereochemical course of the ring closure, with only the beta series being amenable to the proper elaboration of paclitaxel. When C-4 and C-5 are incorporated into a 1,3-dioxane ring instead, the principal stereocontrol element is translocated into the aryl-substituted carbon of the cyclic acetal. To the extent that the Ar group remains equatorially disposed, then proper aldolization will materialize in only one of the four possible diastereomers. Experimental tests that are provided for three of the models are shown to conform to expectations. This analysis of the origin of stereoselectivity has, for the first time, defined the scope and limitations associated with C-ring closure by means of the aldol protocol.

  DOI：

  10.1021/jo981749j
• 作为产物：
  描述：

  (S)-1-[(R)-oxiran-2-yl]prop-2-enol 在 sodium hydroxide 、 水 、 copper(II) sulfate 作用下， 反应 82.5h， 生成 (2R,4S,5R)-5-hydroxy-2-phenyl-4-vinyl-1,3-dioxane
  参考文献：
  名称：

  二乙烯基甲醇的不对称尖锐环氧化。通过区域异构环氧-4-戊烯醇的水解制备赤藓基-D-和-L-4-戊烯醇

  摘要：

  详细描述了仲乙烯基非手性烯丙醇二乙烯基甲醇（1）的不对称Sharpless环氧化反应。环氧化以高对映体控制和非对映选择进行。使所得的1，2-环氧-4-戊烯-3-醇2平衡以提供内部环氧化物5。区域异构体2和5的水解分别以高选择性提供了赤型-4-戊烯醇3的相反对映异构体。描述了3的几种衍生物，以及较少的立体选择性路线的结果-来自D-甘油醛丙酮化物（10）-提供了苏氨酸的NMR数据系列。-报告了二乙烯基甲醇（1）的急性毒性，以及通过Ames试验确定的1，L- 2和L- 5的致突变性。

  DOI：

  10.1016/s0040-4020(01)96130-7

文献信息

• C-glycosphingolipid precursors via iodocyclization of homoallyic trichloroacetimidates
  作者：Ahmad S. Altiti、David R. Mootoo

  DOI：10.1016/j.carres.2015.02.005

  日期：2015.4

  The iodocyclization of homoallylic trichloroacetimidates derived from alpha-C-allyl galactoside were investigated. In line with the stereochemical trend observed for less substituted non-glycosylated frameworks, E and Z substrates delivered stereoselectively the 1,3-anti and 1,3-syn amino alcohol motifs, respectively. These products are advanced precursors to C-glycosides of the potent immunostimulatory

  研究了源自α-C-烯丙基半乳糖苷的高烯丙基三氯乙酰亚胺酯的碘环化。与较少取代的非糖基化框架观察到的立体化学趋势一致，E 和 Z 底物分别立体选择性地递送 1,3-anti 和 1,3-syn 氨基醇基序。这些产品是强效免疫刺激糖脂 KRN7000 的 C-糖苷的高级前体。
• Diastereoselective Ring-Closing Metathesis as a Means to Construct Medium-Sized Cyclic Ethers: Application to the Synthesis of a Photoactivatable Gambierol Derivative
  作者：Yu Onodera、Kazuaki Hirota、Yuto Suga、Keiichi Konoki、Mari Yotsu-Yamashita、Makoto Sasaki、Haruhiko Fuwa

  DOI：10.1021/acs.joc.6b01302

  日期：2016.9.16

  describes a concise synthesis of six- to eight-membered α,α′-substituted cyclic ethers by exploiting diastereoselective ring-closing metathesis (RCM) of 1,4-pentadien-3-yl ether derivatives. The RCM precursors could be efficiently prepared via a vinylation of the corresponding α-acetoxy ether derivatives using divinylzinc. Diastereoselective RCM of 1,4-pentadien-3-yl ether derivatives afforded a series

  本文介绍了通过利用1,4-戊二烯-3-基醚衍生物的非对映选择性闭环复分解（RCM）合成六至八元的α，α'-取代的环醚的方法。可以使用二乙烯基锌通过相应的α-乙酰氧基醚衍生物的乙烯基化来有效地制备RCM前体。1,4-戊二烯-3-基醚衍生物的非对映选择性RCM提供一系列具有中等至良好非对映选择性的六至八元α，α'-取代的环状醚。非对映选择性RCM的立体化学结果似乎取决于所锻造的环的结构。六元和七元环醚的非对映选择性似乎在很大程度上受动力学控制，而与催化剂的反应性无关，而八元环醚的催化活性可以控制。最后，将非对映选择性RCM化学方法用于合成生物素标记的甘比罗尔可光活化衍生物。
• Regiocontrol in the Oxidative Radical Fragmentation of Benzilidene Acetals and Its Mechanistic Implications
  作者：James McNulty、Jeff Wilson、Amanda C. Rochon

  DOI：10.1021/jo035223x

  日期：2004.1.1

  The NBS-mediated oxidative fragmentation of benzilidene acetals has been investigated with mechanistic probes 12, 14, and 18 designed to discriminate between the possible competitive pathways. Results indicate that fragmentation of the initial benzylic radical 19 does not occur spontaneously but that oxidation proceeds rapidly to give the benzyl bromide 20, which then fragments via a polar pathway

  亚苄缩醛的NBS-介导的氧化碎片已被调查与机械探针12，14，和18设计了可能的竞争性途径之间进行区分。结果表明初始苄基基团19的断裂不是自发发生的，而是氧化迅速进行而得到苄基溴化物20，然后该苄基溴化物通过极性途径断裂。通过将烯丙醇掺入到苯并乙二醛缩醛中，首次证明了片段化中的反向区域特异性。
• Synthesis of the C11−C23 Fragment of Spirastrellolide A. A Ketal-Tethered RCM Approach to the Construction of Spiroketals
  作者：Jia Liu、Richard P. Hsung

  DOI：10.1021/ol050653q

  日期：2005.5.1

  [reaction: see text]. The synthesis of the C11-C23 fragment in spirastrellolide A is described here featuring a ketal-tethered RCM as an alternative approach to the construction of spiroketals.

  [反应：请参见文字]。本文描述了螺旋藻内酯A中C11-C23片段的合成，其特征为缩酮连接的RCM，作为螺环酮构建的替代方法。
• Erythrose sesqui-acetals as electrophiles. 2-Deoxy-C-nucleosides from D-glucose.
  作者：Robin Polt、Thusitha Wijayarathe

  DOI：10.1016/s0040-4039(00)93472-5

  日期：1991.9

  Cleavage of glucosides with NalO4 in MeOH furnishes sesqui-acetals (protected dialdehydes). Olefination of these substrates, followed by endocyclic oxymercuration-demercuration furnishes substituted tetrahydrofurans (1,2-dideoxy-1-aryl-D-ribofuranoses). Proper choice of protecting groups can affect the face selectivity of the oxymercuration step to provide only the desired beta-C-anomer.