6-Carbomethoxy-6-methyl-7-(5-oxazolyl)-1,4-dioxaspiro<4.4>non-7-ene | 123597-49-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 6-Carbomethoxy-6-methyl-7-(5-oxazolyl)-1,4-dioxaspiro<4.4>non-7-ene
• 英文别名: methyl 9-methyl-8-(1,3-oxazol-5-yl)-1,4-dioxaspiro[4.4]non-7-ene-9-carboxylate
• CAS: 123597-49-9
• 化学式: C₁₃H₁₅NO₅
• 分子量: 265.266
• InChiKey: SDFWEPWHKTXEON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.38
• 重原子数：
  19.0
• 可旋转键数：
  2.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  70.79
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  6-Carbomethoxy-6-methyl-7-(5-oxazolyl)-1,4-dioxaspiro<4.4>non-7-ene 在 草酰氯 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 2.67h， 生成 (R*,S*)-6-Methyl-7-(5-oxazolyl)-α-1-(Z)-propenyl-α-1-propynyl-1,4-dioxaspiro<4.4>non-7-ene-6-methanol
  参考文献：
  名称：

  Total synthesis of (.+-.)-gnididione and (.+-.)-isognididione

  摘要：

  DOI：

  10.1021/jo00288a034
• 作为产物：
  描述：

  6-Carbomethoxy-6-methyl-7-(5-oxazolyl)-1,4-dioxaspiro<4.4>nonane 在 phenyltrimethylammonium tribromide 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 氯仿 、 苯 为溶剂， 反应 73.0h， 生成 6-Carbomethoxy-6-methyl-7-(5-oxazolyl)-1,4-dioxaspiro<4.4>non-7-ene
  参考文献：
  名称：

  Total synthesis of (.+-.)-gnididione and (.+-.)-isognididione

  摘要：

  DOI：

  10.1021/jo00288a034

文献信息

• Enynones in Organic Synthesis. 6. Synthesis of Spirocyclic Methylenecyclopentenones and Analogs of the Methylenomycin Class of Antibiotics. Mechanism of Phenol Catalysis
  作者：Peter A. Jacobi、Lisa M. Armacost、Harry L. Brielmann、Reginald O. Cann、Joseph I. Kravitz、Michael J. Martinelli

  DOI：10.1021/jo00097a035

  日期：1994.9

  Spirocyclic methylenecyclopentenones of general structure 18 were prepared in a single step from bis-acetylenic alcohols 29 by a process involving initial oxy-Cope rearrangement to afford (Z)-enynones 30-Z followed by electrocyclic ring closure. Mechanistic studies indicate that the initial step leading from 30-Z to 18 is a thermal 1,5-prototropic shift to afford dienols which can cyclize by a symmetry-allowed (pi(4)s + sigma(2)s + pi(2)a) process. This last step is catalyzed by certain phenols having low oxidation potentials, most likely by a mechanism involving single electron transfer. Dramatic rate enhancements were also observed for the cyclization of simple enynones 37 to methylenecyclopentenones 39 upon catalysis with either a-tocopherol (vitamin E, 40) or tert-butylcatechol(41). Further enhancements in both rate and yield were obtained under conditions of photoassisted single electron transfer (PET), which afforded 39 in yields of 80-98%.
• JACOBI, PETER A.;SELNICK, HAROLD G., J. ORG. CHEM., 55,(1990) N, C. 202-209
  作者：JACOBI, PETER A.、SELNICK, HAROLD G.

  DOI：——

  日期：——