tricyclo<4.4.1.1^2,5>dodeca-3,7,9-trien-11-one | 4668-70-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: tricyclo<4.4.1.1^2,5>dodeca-3,7,9-trien-11-one
• 英文别名: tricyclo[4.4.1.1^2,5]dodeca-3,7,9-trien-11-one；(1S,2S,5R,6R)-tricyclo[4.4.1.12,5]dodeca-3,7,9-trien-11-one
• CAS: 4668-70-6
• 化学式: C₁₂H₁₂O
• 分子量: 172.227
• InChiKey: INLAFCWZCJGTFM-CKIJPRSSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tricyclo<4.4.1.1^2,5>dodeca-3,7,9-trien-11-one 在 菲 作用下， 以 乙醚 为溶剂， 生成
  参考文献：
  名称：

  Photochemical reaction of bridged cyclohepta-3,5-dienone systems

  摘要：

  DOI：

  10.1021/ja00757a083
• 作为产物：
  描述：

  tribromocycloheptanone 在 lithium carbonate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 73.0h， 生成 tricyclo<4.4.1.1^2,5>dodeca-3,7,9-trien-11-one
  参考文献：
  名称：

  The configuration and conformation of the tricyclo[4.4.1.12,5]dodecan-11-ols determined by1H NMR spectroscopy using the shift reagent Eu(fod)3

  摘要：

  AbstractThe isomeric tricyclo[4.4.1.12,5]dodecan‐11‐ols have been synthesized from the (6+4) cycloaddition product of tropone with cyclopentadiene. The configuration and conformation of each isomer was determined from the proton shift gradients induced in the olefinic proton signals in the 1H NMR spectra of intermediate compounds by Eu(fod)3.

  DOI：

  10.1002/mrc.1270150324

文献信息

• Bicyclofulvene—VI
  作者：Reinhard W. Hoffman、Johannes Becherer

  DOI：10.1016/0040-4020(78)80143-4

  日期：1978.1

  Ketene imminium ion (4), diphenyl ketene, tosyl isocyanate and tetracyanoethylene add selectively to the semicyclic double bond of 1. This is interpreted to result from the polarity of the semicyclic double bond in 1.

  烯酮亚铵离子（4），二苯基乙烯酮，甲苯磺酰基异氰酸酯和四氰乙烯选择性地添加到的semicyclic双键1。这被解释为是由1中的半环双键的极性引起的。
• Application of Lewis Acid Catalyzed Tropone [6+4] Cycloadditions to the Synthesis of the Core of CP-225,917
  作者：Ljubomir Isakovic、James A. Ashenhurst、James L. Gleason

  DOI：10.1021/ol016814h

  日期：2001.12.1

  The carbocyclic core of CP-225,917 and CP-263,114 is accessible through the [6+4] cycloaddition of a tropone with a 2-substituted cyclopentadiene. Examination of this reaction has revealed for the first time that this cycloaddition process is catalyzed by Lewis acids, including lanthanide triflates. Cycloadditions of several mono-, di-, and trisubstituted tropones with 2-silyloxycyclopentadienes using

  CP-225,917和CP-263,114的碳环核可通过将6-环己二烯与2个取代的环戊二烯进行[6 + 4]环加成而获得。该反应的检验首次揭示该环加成过程是由路易斯酸，包括镧系三氟甲磺酸酯催化的。发现使用ZnCl（2）催化与2-甲硅烷氧基环戊二烯的几个单，二和三取代的托环酮的环加成反应可进行良好的收率，在许多情况下，具有非对映选择性。随后转化为CP分子的核心涉及三环二酮的位点选择性Baeyer-Villiger氧化，然后进行同消除过程。[反应：看文字]
• Stereospecific Synthesis And Acetolysis of <i>anti</i>-Tricyclo[4.4.1.12′5]Dodecan-11-yl And Related Derivatives
  作者：J. Hay Wood-Farmer、B. T. Friedlander、A. Crawford、L. M. Thompson、and W. Wetzer

  DOI：10.1139/v75-437

  日期：1975.10.15

  Stereospecific conversion of tricyclo[4.4.1.1^2,5]dodecan-11-one and of several related unsaturated and cyclopropanated ketones into syn or anti alcohols is described. Acetolysis of anti-tricyclo[4.4.1.1²'⁵]dodecan-11-yl p-bromobenzenesulfonate, anti-tricyclo[4.4.1.1²'⁵]dodec-3-en-11-yl p-bromobenzenesulfonate, anti;-tetracyclo[5.4.1.1^2,6.0^3,5]tridecan-12-yl p-bromobenzenesulfonate each proceeds at about the same rate as other equatorial cyclohexyl p-bromobenzenesulfonates to give complex mixtures of rearranged acetates and hydrocarbons. No evidence for neighboring group participation by the remote double bond or cyclopropane ring in these esters was found. The stereochemically interesting ketone reductions, the unambiguous structural proofs of the reduction products, and possible explanations of the solvolysis rates are discussed.

  本文描述了将三环[4.4.1.1^2,5]十二酮及几种相关的不饱和和环丙基酮立体特异性地转化为顺式或反式醇。反式三环[4.4.1.1²'⁵]十二酮基对-溴苯磺酸酯、反式三环[4.4.1.1²'⁵]十三碳-3-烯基对-溴苯磺酸酯、反式四环[5.4.1.1^2,6.0^3,5]十三碳-12-基对-溴苯磺酸酯的乙酸解反应速率与其他赤道环己基对-溴苯磺酸酯大致相同，产生复杂的重排醋酸酯和碳氢化合物混合物。没有发现这些酯中远离双键或环丙烷环的相邻基团参与。讨论了立体化学有趣的酮还原、还原产物的明确结构证明和溶剂解离速率的可能解释。
• A synthetic approach to bicyclo[6.2.1]undecane ring systems
  作者：Mauricio Gomes Constantino、Kleber Thiago de Oliveira、Adilson Beatriz、Gil Valdo José da Silva

  DOI：10.1016/s0040-4039(03)00377-0

  日期：2003.3

  A synthesis of a functionalized bicyclo[6.2.1]undecane, N-(7-hydroxymethyl-bicyclo[6.2.1]undeca-3,5,9-trien-2-yl)-4-methyl-benzenesulfonamide, is described. Starting with a [6+4] cycloaddition between cyclopentadiene and cycloheptatrienone, the final product was prepared in five steps with an overall 37% yield. The remarkable resistance to hydrolysis of an intermediate lactam was overcome by tosylating

  描述了官能化的双环[6.2.1]十一烷，N-（7-羟甲基-双环[6.2.1] undeca-3,5,9-三烯-2-基）-4-甲基-苯磺酰胺的合成。从环戊二烯与环庚三烯酮之间的[6 + 4]环加成反应开始，分五步制备最终产品，总收率37％。通过将甲苯磺酸甲苯磺酸酯化并用LiAlH 4还原，可以克服中间体内酰胺的显着抗水解性。
• The Effect of Leaving Group Orientation on Solvolytic Cope Rearrangements. A Study of<i>exo</i>-Tricyclo[4.4.1.1^2,5]dodeca-3,7,9-trien-11-yl Tosylates and Derivatives
  作者：Shô Itô、Isamu Itoh、Yutaka Fujise、Tetsuo Nakatsu、C. A. Senkler、P. v. R. Schleyer

  DOI：10.1246/bcsj.51.2379

  日期：1978.8

  rearrangements, probably occurring after ionization. On the other hand, anti-18-OTs and anti-23-OTs solvolyze at rates ca. 102 times slower than those predicted by Foote-Schleyer calculations. Presumably the anti derivatives of 18-OTs, 20-OTs, 23-OTs, and the tetrahydro tosylate (22-OTs) suffer steric hindrance to ionization. Product formation from anti-18-OTs (Table 3) and anti-19-OTs in acetic acid and 75%

  描述了高度受阻的标题化合物的衍生物的合成和溶剂分解行为，exo-Tricyclo[4.4.1.12,5]dodeca-3,7,9-trien-syn-yl tosylate (syn-18-OTs) 和相应的 perhydro衍生物，syn-23-OTs，以与 Foote-Schleyer 计算预测的速率合理一致的速率溶解。syn-18-OTs，及其二氢衍生物，syn-19-OTs 和 syn-20-OTs，完全给出重排产物分别在乙酸和 75% 二恶烷、80% 丙酮和 75% 二恶烷中溶剂分解（表 2）。这些产物可以用正常的阳离子重排来解释，可能发生在电离后。另一方面，抗 18-OTs 和抗 23-OTs 的溶解速率约为。比 Foote-Schleyer 计算预测的慢 102 倍。大概是 18-OTs、20-OTs、23-OTs 的反衍生物，和四氢甲苯磺酸盐 (22-OTs) 受到电离的空间位阻。乙酸和