(Z)-[2R,4S,5R]-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylonitrile | 501373-21-3

• 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: (Z)-[2R,4S,5R]-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylonitrile
• 英文别名: (Z)-3-(5-(R)-hydroxy-2-(R)-phenyl-[1,3]dioxan-4-(S)-yl)acrylonitrile；(Z)-3-[(2R,4S,5R)-5-hydroxy-2-phenyl-1,3-dioxan-4-yl]prop-2-enenitrile
• CAS: 501373-21-3
• 化学式: C₁₃H₁₃NO₃
• 分子量: 231.251
• InChiKey: QWKZWFYUZYWOOL-PBRGRUASSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  17
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  62.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (Z)-[2R,4S,5R]-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylonitrile 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 14.83h， 生成 ((2R,4aR,6R,7S,7aS)-6-Imidazol-1-yl-2-phenyl-tetrahydro-furo[3,2-d][1,3]dioxin-7-yl)-acetonitrile
  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 甲苯 为溶剂， 反应 14.0h， 生成 (Z)-[2R,4S,5R]-3-(5-hydroxy-2-phenyl-[1,3]dioxane-4-yl)-acrylonitrile
  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

• 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.