(1R,6R)-9-(Z-bromomethylene)-7-oxabicyclo[4.3.1]dec-2-en-8-one | 1358918-29-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (1R,6R)-9-(Z-bromomethylene)-7-oxabicyclo[4.3.1]dec-2-en-8-one
• 英文别名: (1R,6R,9Z)-9-(bromomethylidene)-7-oxabicyclo[4.3.1]dec-2-en-8-one
• CAS: 1358918-29-2
• 化学式: C₁₀H₁₁BrO₂
• 分子量: 243.1
• InChiKey: IXWVUEMATHZFEC-GCICIJSESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (5S,2Z)-1-(methoxycarbonyloxy)nona-2,8-dien-5-ol 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 rhodium(II) perfluorobutyrate dimer 、 偶氮二甲酸二异丙酯 、 三苯基膦 、 lithium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 1,1,2-三氯乙烷 为溶剂， 反应 7.0h， 生成 (1R,6R)-9-(Z-bromomethylene)-7-oxabicyclo[4.3.1]dec-2-en-8-one
  参考文献：
  名称：

  Halocarbocyclization Entry into the Oxabicyclo[4.3.1]decyl Exomethylene-δ-Lactone Cores of Linearifolin and Zaluzanin A: Exploiting Combinatorial Catalysis

  摘要：

  A streamlined entry into the sesquiterpene lactone (SQL) cores of linearifolin and zaluzanin A is described. Stereochemistry is controlled through transformations uncovered by ISES (In Situ Enzymatic Screening). Absolute stereochemistry derives from kinetic resolution of 5-benzyloxypentene-1,2-oxide, utilizing a,beta-pinene-derived-Co(III)-salen. Relative stereochemistry (1,3-cis-fusion) is set via formal halometalation/carbocyclization, mediated by [Rh(O2CC3F7)(2)](2)/LiBr. Subsequent ring-closing metathesis (RCM-Grubbs II) yields the title exomethylene-delta-lactone SQL cores. In complementary fashion, RCM with Grubbs-I catalyst provides the oxabicyclo[3.3.1]nonyl core of xerophilusin R and zinagrandinolide.

  DOI：

  10.1021/ol203088g

文献信息

• Halocarbocyclization Entry into the Oxabicyclo[4.3.1]decyl Exomethylene-δ-Lactone Cores of Linearifolin and Zaluzanin A: Exploiting Combinatorial Catalysis
  作者：Sandeep K. Ginotra、Jacob A. Friest、David B. Berkowitz

  DOI：10.1021/ol203088g

  日期：2012.2.17

  A streamlined entry into the sesquiterpene lactone (SQL) cores of linearifolin and zaluzanin A is described. Stereochemistry is controlled through transformations uncovered by ISES (In Situ Enzymatic Screening). Absolute stereochemistry derives from kinetic resolution of 5-benzyloxypentene-1,2-oxide, utilizing a,beta-pinene-derived-Co(III)-salen. Relative stereochemistry (1,3-cis-fusion) is set via formal halometalation/carbocyclization, mediated by [Rh(O2CC3F7)(2)](2)/LiBr. Subsequent ring-closing metathesis (RCM-Grubbs II) yields the title exomethylene-delta-lactone SQL cores. In complementary fashion, RCM with Grubbs-I catalyst provides the oxabicyclo[3.3.1]nonyl core of xerophilusin R and zinagrandinolide.