(E)-(2R,4S,5R)-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylic acid ethyl ester | 501373-19-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (E)-(2R,4S,5R)-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylic acid ethyl ester
• 英文别名: (E)-3-(5-(R)-hydroxy-2-(R)-phenyl-[1,3]dioxan-4-(S)-yl)acrylic acid ethyl ester；ethyl (E)-3-[(2R,4S,5R)-5-hydroxy-2-phenyl-1,3-dioxan-4-yl]prop-2-enoate
• CAS: 501373-19-9
• 化学式: C₁₅H₁₈O₅
• 分子量: 278.305
• InChiKey: UQEZCCXIGASYQZ-ZBLHKVTASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  65
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (E)-(2R,4S,5R)-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylic acid ethyl ester 在 4-二甲氨基吡啶 、 偶氮二异丁腈 、 三苯基氢化锡 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 40.0h， 生成 ((2R,4aR,6R,7S,7aS)-6-Imidazol-1-yl-2-phenyl-tetrahydro-furo[3,2-d][1,3]dioxin-7-yl)-acetic acid ethyl ester
  参考文献：
  名称：

  Stereochemical control in radical cyclization routes to N-glycosides: role of protecting groups and of the configuration (E versus Z) of the acceptors

  摘要：

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl or exo-hept-6-enyl type radical cyclization when a suitable radical acceptor (e.g. alpha,beta-unsaturated ester. oxime ether or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thioates with such acceptors. upon addition to excess of a good hydride donor (reverse addition), undergo moderately efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either C-2-carbon or C-2-amino substituents are formed. In the exo-hept-6-enyl cyclizations the (Z)-olefin acceptors give excellent stereoselectivity in the generation of the C-2 stereogenic center: only altro-isomers are formed. In all cases both alpha- and beta-glycosides are obtained with a moderate preference for the latter. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.07.013
• 作为产物：
  描述：

  4,6-O-benzylidene-D-glucose 在 sodium hydroxide 、 sodium periodate 作用下， 以 乙二醇二甲醚 为溶剂， 反应 26.0h， 生成 (E)-(2R,4S,5R)-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylic acid ethyl ester
  参考文献：
  名称：

  Stereochemical control in radical cyclization routes to N-glycosides: role of protecting groups and of the configuration (E versus Z) of the acceptors

  摘要：

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl or exo-hept-6-enyl type radical cyclization when a suitable radical acceptor (e.g. alpha,beta-unsaturated ester. oxime ether or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thioates with such acceptors. upon addition to excess of a good hydride donor (reverse addition), undergo moderately efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either C-2-carbon or C-2-amino substituents are formed. In the exo-hept-6-enyl cyclizations the (Z)-olefin acceptors give excellent stereoselectivity in the generation of the C-2 stereogenic center: only altro-isomers are formed. In all cases both alpha- and beta-glycosides are obtained with a moderate preference for the latter. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.07.013

文献信息

• Direct Kinetic Formation of Nonanomeric [6.5]-Spiroketals in Aqueous Media
  作者：Daniele Castagnolo、Irene Breuer、Petri M. Pihko

  DOI：10.1021/jo702022u

  日期：2007.12.1

  precursors under acid catalysis was studied using four differently substituted systems. In all cases, the exclusive formation of the anomeric isomer was observed under equilibrating conditions. However, the formation of the nonanomeric spiroketal isomer was observed if the reaction was performed under kinetic conditions using an appropriately tuned acid. Water had a dramatic accelerating effect on the spiroketalization

  使用四种不同取代的体系研究了在酸催化下由混合的缩酮醇前体直接形成螺环酮的动力学过程。在所有情况下，在平衡条件下均观察到异头异构体的排他性形成。但是，如果反应是在动力学条件下使用适当调节的酸进行的，则观察到非端基螺酮异构体的形成。水对在THF中进行的螺酮缩合反应具有显着的加速作用，在THF水溶液中获得最高产率的非端基异构体产物。所述非端基异构体/端基异构体产物的比例也受到取代基和起始醇的立体化学的强烈影响。
• A New Reaction Manifold for the Barton Radical Intermediates:  Synthesis of <i>N</i>-Heterocyclic Furanosides and Pyranosides via the Formation of the C₁−C₂ Bond
  作者：Jong Uk Rhee、Brian I. Bliss、T. V. RajanBabu

  DOI：10.1021/ja028617z

  日期：2003.2.1

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl- or exo-hept-6-enyl-type radical cyclization when a suitable radical acceptor (e.g., alpha,beta-unsaturated ester, oxime ether, or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thiourethanes with such acceptors, upon addition to excess of a good hydride donor (reverse addition), undergo efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either a C(2)()-amino or a C(2)()-carbon substituent are formed.
• Stereochemical control in radical cyclization routes to N-glycosides: role of protecting groups and of the configuration (E versus Z) of the acceptors
  作者：Jong Uk Rhee、Brian I. Bliss、T.V. RajanBabu

  DOI：10.1016/j.tetasy.2003.07.013

  日期：2003.10

  The first radical intermediate in the thiourethane-mediated deoxygenation of an alcohol (Barton-McCombie reaction) can participate in an exo-hex-5-enyl or exo-hept-6-enyl type radical cyclization when a suitable radical acceptor (e.g. alpha,beta-unsaturated ester. oxime ether or hydrazone) is appropriately placed. Carbohydrate-derived imidazolyl and triazolyl thioates with such acceptors. upon addition to excess of a good hydride donor (reverse addition), undergo moderately efficient cyclization reactions to give N-heterocyclic furanosides, and, surprisingly even N-pyranosides. Depending on the acceptor, glycosides with either C-2-carbon or C-2-amino substituents are formed. In the exo-hept-6-enyl cyclizations the (Z)-olefin acceptors give excellent stereoselectivity in the generation of the C-2 stereogenic center: only altro-isomers are formed. In all cases both alpha- and beta-glycosides are obtained with a moderate preference for the latter. (C) 2003 Elsevier Ltd. All rights reserved.