2,4-bis((trimethylsilyl)oxy)-1-butene | 117201-93-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 2,4-bis((trimethylsilyl)oxy)-1-butene
• 英文别名: 2,2,8,8-tetramethyl-4-methylene-3,7-dioxa-2,8-disilanonane；Trimethyl(3-trimethylsilyloxybut-3-enoxy)silane
• CAS: 117201-93-1
• 化学式: C₁₀H₂₄O₂Si₂
• 分子量: 232.47
• InChiKey: JKYRWNRHDBUCCE-UHFFFAOYSA-N

物化性质

• 沸点：
  217.0±23.0 °C(Predicted)
• 密度：
  0.852±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2,4-bis((trimethylsilyl)oxy)-1-butene 、 原甲酸三乙酯 在 四氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以60%的产率得到2-ethoxytetrahydropyran-4-one
  参考文献：
  名称：

  Chemistry of aldolate dianions. β-Silyloxy silyl enol ethers as bifunctional nucleophilic equivalents for oxygen heterocycle synthesis

  摘要：

  DOI：

  10.1016/s0040-4039(00)94538-6
• 作为产物：
  描述：

  三甲基氯硅烷 、 4-羟基-2-丁酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 三氟乙酸 为溶剂， 生成 2,4-bis((trimethylsilyl)oxy)-1-butene
  参考文献：
  名称：

  Convergent One-Pot Oxidative [n+ 1] Approaches to Spiroacetal Synthesis

  摘要：

  Two one-pot oxidative annulative approaches to spiroacetal synthesis are described. One approach uses a Lewis acid mediated Ferrier reaction in the fragment-coupling stage followed by DDQ-promoted oxidative carbon-hydrogen bond cleavage and cyclization. An alternative approach employs a Heck reaction for fragment coupling followed by DDQ-mediated enone formation and cyclization. These strategies provide convergent routes to common subunits in natural products, medicinal agents, and chemical libraries under mild reaction conditions.

  DOI：

  10.1021/acs.orglett.5b01736

文献信息

• Chemistry of dioxenium cations. Synthetic and mechanistic studies on the stereocontrolled formation of tetrahydropyrans from homoallylic alcohols and ortho esters
  作者：Francoise Perron-Sierra、Michele A. Promo、Van A. Martin、Kim F. Albizati

  DOI：10.1021/jo00021a043

  日期：1991.10

  Despite their long history, dioxenium cations are underutilized reactive synthetic intermediates. It was found that ortho esters and homoallylic alcohols in the presence of Lewis acids provide 4-heterosubstituted pyranosides in a stereoselective manner. The mechanistic course of events was supported by control experiments and synthesis of a putative mixed ortho ester intermediate which exhibited identical reactivity. A transition state for termination of the dioxenium cation-olefin cyclization is proposed, involving intramolecular delivery of chloride by a coordinated tin species. Structure-reactivity relationships indicate that a cation-stabilizing substituent (alkyl or alkoxy) at the internal position of the olefin is required for cyclization. A variety of 3-alkyl-substituted homoallylic alcohols cyclize cleanly to substituted 2-alkoxytetrahydropyrans in good yield. beta-silyloxy silyl enol ethers were found to smoothly provide 4-oxotetrahydropyranosides when subjected to the same reaction conditions. For these substrates, the course of the cyclization proceeds in a different manner involving a rapid intermolecular Mukaiyama aldol condensation followed by transacetalization.
• Generation, chemical stability, and reactivity of aldolate dianions
  作者：Van A. Martin、Kim F. Albizati

  DOI：10.1021/jo00260a041

  日期：1988.12
• Van Martin; Murray, Desmond H.; Pratt, Norman E., Journal of the American Chemical Society, 1990, vol. 112, # 19, p. 6965 - 6978
  作者：Van Martin、Murray, Desmond H.、Pratt, Norman E.、Zhao, Yun-Bo、Albizati, Kim F.

  DOI：——

  日期：——
• J. ORG. CHEM., 53,(1988) N5, C. 5986-5988
  作者：

  DOI：——

  日期：——
• MARTIN, VAN A.;PERRON, FRANCOISE;ALBIZATI, KIM F., TETRAHEDRON LETT., 31,(1990) N, C. 301-304
  作者：MARTIN, VAN A.、PERRON, FRANCOISE、ALBIZATI, KIM F.

  DOI：——

  日期：——