3-(E)-{5-(S)-[2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-(imidazole-1-carbonothioyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-(S)-yl}-acrylonitrile | 501373-33-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(E)-{5-(S)-[2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-(imidazole-1-carbonothioyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-(S)-yl}-acrylonitrile
• CAS: 501373-33-7
• 化学式: C₂₀H₃₁N₃O₄SSi
• 分子量: 437.635
• InChiKey: JVSYNKFWIGXEHQ-CVHJSEFTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.02
• 重原子数：
  29.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  78.53
• 氢给体数：
  0.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  3-(E)-{5-(S)-[2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-(imidazole-1-carbonothioyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-(S)-yl}-acrylonitrile 在 偶氮二异丁腈 、 三苯基氢化锡 作用下， 以 苯 为溶剂， 反应 3.17h， 生成 [(3aS,4R,6R,7S,7aS)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-6-imidazol-1-yl-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yl]-acetonitrile 、 [(3aS,4R,6S,7S,7aS)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-6-imidazol-1-yl-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yl]-acetonitrile 、 [(3aS,4R,6R,7R,7aS)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-6-imidazol-1-yl-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-7-yl]-acetonitrile 、 [(3aS,4R,6S,7R,7aS)-4-(tert-Butyl-dimethyl-silanyloxymethyl)-6-imidazol-1-yl-2,2-dimethyl-tetrahydro-[1,3]dioxolo[4,5-c]pyran-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：

  N,N'-硫羰基二咪唑 、 3-(E)-{5-(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-(S)-yl}-acrylonitrile 在 4-二甲氨基吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 22.0h， 以88%的产率得到3-(E)-{5-(S)-[2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-(imidazole-1-carbonothioyloxy)-ethyl]-2,2-dimethyl-[1,3]dioxolan-4-(S)-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.