(5RS,6SR)-5,6-diphenylcycloheptane-1,3-dione | 222629-92-7

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二芳基庚烷
• 英文名称: (5RS,6SR)-5,6-diphenylcycloheptane-1,3-dione
• 英文别名: (5R,6S)-5,6-diphenylcycloheptane-1,3-dione；cis-3,4-diphenylcycloheptan-1,6-dione；(5S,6R)-5,6-diphenylcycloheptane-1,3-dione
• CAS: 222629-92-7
• 化学式: C₁₉H₁₈O₂
• 分子量: 278.351
• InChiKey: YHHOZZARKDOKTJ-KDURUIRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.26
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  cis-2-tert-butyldimethylsiloxy-4-methoxy-6,7-diphenylcyclohepta-1,4-diene 在 盐酸 、 水 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以71%的产率得到(5RS,6SR)-5,6-diphenylcycloheptane-1,3-dione
  参考文献：
  名称：

  Reactions of Fischer Carbene Complexes with Siloxydienes: Formation of Cycloheptadiene and Cyclopentene Derivatives—Formal [2+1] Cycloaddition Followed by Cope Rearrangement Versus Formal [3+2] Cycloaddition with or without Preceding Carbene-Ligand Metathesis

  摘要：

  Thermal reactions of the alpha,beta-unsaturated Fischer carbene complexes 3-5 with the siloxydienes 6 and 7 mainly furnished the expected cyclohepta-1,4-dienes such as 9, 10, 12, 14, and 15, whose formation is explained by a formal [2+1] cycloaddition followed by Cope rearrangement. The rather electron-rich carbene complex 5 also afforded the cyclopentene derivatives II and 16 as by-products, which are probably formed by two distinct mechanisms. Single diastereomers of the cyclopentene derivatives 17 and 18 were isolated as the exclusive products of the reactions of 3 and 4, respectively, with the donor/acceptor-substituted 1,3-diene 8. This process is interpreted as a metalla Diels-Alder reaction to form a chromacyclohexene intermediate 25, which subsequently undergoes fragmentation to give cyclopentene derivatives with the required constitution. Most surprisingly, the reactions of simple carbene complexes 1 or 2 with the siloxydienes 7 or 8 yielded cyclopentene derivatives 19 and 20 that do not contain the carbene ligand of the precursor complexes. Instead, the constitution of the isolated products can be accounted for by a formal diene dimerization with fragmentation of a methylene unit. Their formation can be interpreted by an unprecedented sequence of carbene-ligand metathesis followed by a metalla Diels-Alder reaction and reductive fragmentation. All these results illustrate the great importance of electronic fine-tuning in the precursors involved in reactions of Fischer carbene complexes with 1,S-dienes.

  DOI：

  10.1002/(sici)1521-3765(19990301)5:3<876::aid-chem876>3.0.co;2-t

文献信息

• Preparation of cycloheptane ring by nucleophilic cyclopropanation of 1,2-diketones with bis(iodozincio)methane
  作者：Ryosuke Haraguchi、Yoshiaki Takada、Seijiro Matsubara

  DOI：10.1039/c4ob01474j

  日期：——

  The nucleophilic cyclopropanation of hexa-1,5-diene-3,4-diones with bis(iodozincio)methane afforded the Zn alkoxides of cis-dialkenylcyclopropane-1,2-diols stereoselectively. The subsequent oxy-Cope rearrangement afforded the corresponding Zn alkoxides of 5,6-dialkylcyclohepta-3,7-diene-1,3-diols.

  六-1,5-二烯-3,4-二酮与双（碘嗪）甲烷的亲核环丙烷化可立体选择性地提供顺式-二烯基环丙烷-1,2-二醇的锌醇盐。随后的oxy-Cope重排得到5,6-二烷基环庚-3,7-二烯-1,3-二醇的相应的Zn醇盐。
• Preparation of a Cycloheptane Ring from a 1,2-Diketone with High Stereoselectivity
  作者：Yoshiaki Takada、Kenichi Nomura、Seijiro Matsubara

  DOI：10.1021/ol102237b

  日期：2010.11.19

  Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane gave zinc alkoxides of cis-5,6-dialkylcyclohepta-3,7-diene-1,3-diol in good yields at room temperature. The reaction proceeded with high stereospecificity. Bis(iodozincio)methane converted the diketone into the cis-divinylcyclopropane-1,2-diol stereoselectively; this diol transformed into the corresponding cycloheptane derivative

  用双（碘并甲烷）甲烷处理1,6-二烷基六-1,5-二烯-3,4-二酮可得到顺式-5,6-二烷基环庚-3,7-二烯-1,3-二醇的锌醇盐在室温下收率。反应以高立体特异性进行。双（碘嗪）甲烷将二酮立体选择性地转化为顺式-二乙烯基环丙烷-1，2-二醇。该二醇经Cope重排立体定向转化为相应的环庚烷衍生物。
• Rapid Preparation of Cycloheptane Ring from 1,2-Diketone and Bis(iodozincio)methane via Oxy-Cope Rearrangement Using Microflow System
  作者：Ryosuke Haraguchi、Yoshiaki Takada、Seijiro Matsubara

  DOI：10.1246/cl.2012.628

  日期：2012.6.5

  Treatment of 1,6-dialkylhexa-1,5-diene-3,4-diones with bis(iodozincio)methane at −78 °C for several hours gave cis-dialkenylcyclopropane-1,2-diols which rearranged into the zinc alkoxides of cis-5,...

  1,6-二烷基六-1,5-二烯-3,4-二酮在 -78 °C 下用双（碘锌）甲烷处理数小时，得到顺式二烯基环丙烷-1,2-二醇，其重排为顺式5，...
• Reactions of Fischer Carbene Complexes with Siloxydienes: Formation of Cycloheptadiene and Cyclopentene Derivatives—Formal [2+1] Cycloaddition Followed by Cope Rearrangement Versus Formal [3+2] Cycloaddition with or without Preceding Carbene-Ligand Metathesis
  作者：Matthias Hoffmann、Matthias Buchert、Hans-Ulrich Reißig

  DOI：10.1002/(sici)1521-3765(19990301)5:3<876::aid-chem876>3.0.co;2-t

  日期：1999.3.1

  Thermal reactions of the alpha,beta-unsaturated Fischer carbene complexes 3-5 with the siloxydienes 6 and 7 mainly furnished the expected cyclohepta-1,4-dienes such as 9, 10, 12, 14, and 15, whose formation is explained by a formal [2+1] cycloaddition followed by Cope rearrangement. The rather electron-rich carbene complex 5 also afforded the cyclopentene derivatives II and 16 as by-products, which are probably formed by two distinct mechanisms. Single diastereomers of the cyclopentene derivatives 17 and 18 were isolated as the exclusive products of the reactions of 3 and 4, respectively, with the donor/acceptor-substituted 1,3-diene 8. This process is interpreted as a metalla Diels-Alder reaction to form a chromacyclohexene intermediate 25, which subsequently undergoes fragmentation to give cyclopentene derivatives with the required constitution. Most surprisingly, the reactions of simple carbene complexes 1 or 2 with the siloxydienes 7 or 8 yielded cyclopentene derivatives 19 and 20 that do not contain the carbene ligand of the precursor complexes. Instead, the constitution of the isolated products can be accounted for by a formal diene dimerization with fragmentation of a methylene unit. Their formation can be interpreted by an unprecedented sequence of carbene-ligand metathesis followed by a metalla Diels-Alder reaction and reductive fragmentation. All these results illustrate the great importance of electronic fine-tuning in the precursors involved in reactions of Fischer carbene complexes with 1,S-dienes.