5(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolane-4(S)-carbaldehyde O-methyl-oxime | 501373-34-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolane-4(S)-carbaldehyde O-methyl-oxime
• CAS: 501373-34-8
• 化学式: C₁₅H₃₁NO₅Si
• 分子量: 333.5
• InChiKey: PXZHWHGDKACUNK-YBEJGYGUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.52
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  69.51
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  N,N'-硫羰基二咪唑 、 5(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolane-4(S)-carbaldehyde O-methyl-oxime 以 四氢呋喃 为溶剂， 反应 38.0h， 生成 imidazole-(5S)-carbothioic acid O-{2-(tert-butyl-dimethyl-silanyloxy)-1-(R)-[5-(methoxyimino-methyl)-2,2-dimethyl-[1,3]dioxolan-4-(S)-yl]-ethyl} ester 、 imidazole-5-(S)-carbothioic acid O-{2-(tert-butyl-dimethyl-silanyloxy)-1(R)-[5-(methoxyimino-methyl)-2,2-dimethyl-[1,3]dioxolan-4(S)-yl]-ethyl} ester
  参考文献：
  名称：

  A New Reaction Manifold for the Barton Radical Intermediates:  Synthesis of N-Heterocyclic Furanosides and Pyranosides via the Formation of the C₁−C₂ Bond

  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 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.

  DOI：

  10.1021/ja028617z
• 作为产物：
  描述：

  甲氧基胺盐酸盐 、 5-(tert-butyldimethylsilyloxy)-2,3-isopropylidenedioxy-D-ribofuranose 在 吡啶 作用下， 以 甲醇 为溶剂， 反应 5.5h， 生成 5(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolane-4(S)-carbaldehyde O-methyl-oxime 、 5(R)-[2-(tert-butyl-dimethyl-silanyloxy)-1(R)-hydroxy-ethyl]-2,2-dimethyl-[1,3]dioxolane-4(S)-carbaldehyde O-methyl-oxime
  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