rel-(1S,5R,7R)-5-ethoxycarbonyl-1-phenyl-7-vinyl-2-azabicyclo<3.2.0>heptane-3,4-dione | 60769-89-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: rel-(1S,5R,7R)-5-ethoxycarbonyl-1-phenyl-7-vinyl-2-azabicyclo<3.2.0>heptane-3,4-dione
• 英文别名: rel-(1S,5R,7R)-5-ethoxycarbonyl-1-phenyl-7-vinyl-2-azabicyclo[3.2.0]heptane-3,4-dione；ethyl (1R,5S,7S)-7-ethenyl-3,4-dioxo-1-phenyl-2-azabicyclo[3.2.0]heptane-5-carboxylate
• CAS: 60769-89-3；78215-82-4；130467-49-1；130467-50-4
• 化学式: C₁₇H₁₇NO₄
• 分子量: 299.326
• InChiKey: VBKVEBIMWWQFQV-ZTFRIQLXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  72.5
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  rel-(1S,5R,7R)-5-ethoxycarbonyl-1-phenyl-7-vinyl-2-azabicyclo<3.2.0>heptane-3,4-dione 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以80%的产率得到rel-(1S,5R,7S)-5-ethoxycarbonyl-7-ethyl-1-phenyl-2-azabicyclo<3.2.0>heptane-3,4-dione
  参考文献：
  名称：

  Sano, Takehiro; Horiguchi, Yoshie; Tsuda, Yoshisuke, Chemical and pharmaceutical bulletin, 1987, vol. 35, # 1, p. 9 - 22

  摘要：

  DOI：
• 作为产物：
  描述：

  3-ethoxycarbonyl-2-phenyldioxopyrroline 、 1,3-丁二烯 以 乙二醇二甲醚 为溶剂， 反应 0.75h， 以47.5%的产率得到rel-(1S,5R,7R)-5-ethoxycarbonyl-1-phenyl-7-vinyl-2-azabicyclo<3.2.0>heptane-3,4-dione
  参考文献：
  名称：

  Sano, Takehiro; Horiguchi, Yoshie; Tsuda, Yoshisuke, Chemical and pharmaceutical bulletin, 1987, vol. 35, # 1, p. 9 - 22

  摘要：

  DOI：

文献信息

• Dioxopyrrolines. XLIX. Synthesis of azatropolones via photocycloaddition of 5-aryl-4-ethoxycarbonyl-1H-pyrrole-2,3-diones to acetylenes and ethylenes.
  作者：Takehiro SANO、Yoshie HORIGUCHI、Yoshisuke TSUDA

  DOI：10.1248/cpb.38.3283

  日期：——

  The first synthesis of derivatives of azatropolone, a new nitrogen heterocycle, and some of their chemical properties are described. Two routes to the azatropolone skeletone were developed; one is the photocycloaddition of dioxopyrrolines 1 to acetylenes followed by thermolysis or photolysis of the resulting cyclobutenes 2 to give the azatropolones 7 or 8, and the other is the ring expansion reaction of the cyclobutanes 5 obtained by the photocycloaddition of 1 to olefins followed by 2, 3-dichloro-5, 6-dicyano-1, 4-benzoquinone dehydrogenation of the resulting dihydroazepines 16 to give the azatropolones 7.The azatropolone rapidly consumed diazomethane; thus 7 gave the 3-O-methylazatropolones 18, while 8 gave mixtures of 3-O-methyl-19 and 2-O-methylazatropolones 20. The position of methylation was proved by the unambiguous synthesis of 18 and of 2-O-ethyl derivatives 24 from 16. The azatropolones 7 and 8, when treated with a protonic solvent, readily underwent a ring contraction reaction giving rise to the pyridine-2-carboxylates 29 and 30, respectively, thus demonstrating that the azatropolone nucleus has a strongly electrophilic character.

  首次合成了氮杂环丙烷酮衍生物，并描述了它们的一些化学性质。开发了两条合成氮杂环丙烷酮骨架的途径；一种是将1，4-二氧杂环戊烯与乙炔进行光环加成，然后通过热解或光解得到的环丁烯2生成氮杂环丙烷酮7或8，另一种是通过环扩张反应将1，4-二氧杂环戊烯与烯烃光环加成得到的环丁烷5，然后通过2，3-二氯-5，6-二氰基-1，4-苯醌对得到的二氢氮杂卓16进行脱氢得到氮杂环丙烷酮7。氮杂环丙烷酮迅速消耗重氮甲烷；因此7得到了3-O-甲基氮杂环丙烷酮18，而8得到了3-O-甲基19和2-O-甲基氮杂环丙烷酮20的混合物。甲基化位置通过明确合成18和从16得到的2-O-乙基衍生物24得到了证明。当用质子溶剂处理时，氮杂环丙烷酮7和8容易发生环缩合反应，分别生成吡啶-2-羧酸酯29和30，这表明氮杂环丙烷酮核具有强亲电性。
• Dioxopyrrolines. XLVII. Thermal rearrangements of 7-vinyl derivatives of 1-aryl-5-ethoxycarbonyl-2-azabicyclo(3.2.0)heptane-3,4-diones and their imidates.
  作者：Takehiro SANO、Yoshie HORIGUCHI、Suetaka KAMBE、Kazuhiko TANAKA、Jun'ichi TAGA、Jun TODA、Yoshisuke TSUDA

  DOI：10.1248/cpb.38.1170

  日期：——

  Thermolysis of the 7-vinyl derivative of 1-aryl-5-ethoxycarbonyl-2-azabicyclo[3.2.0]heptane-3, 4-dione caused two different types of skeletal rearrangement depending on the stereochemistry of the 7-vinyl group. The exo-isomer (2) gave the hydroindole (4) by the 1, 3-shift of a C1-C7 bond to the vinyl group (path A reaction), while the endo-isomer (3) gave the 7-azabicyclo[4.2.1]nonane (5) by the Cope rearrangement (path B reaction). The product on thermolysis of the corresponding imidate also depends on the stereochemistry of the 7-vinyl group. The endo-isomer (13) gave the Cope product (12), while the exo-isomer (14) gave the dihydropyridone (16), which is produced by the 1, 3-shift of the C1-C7 bond to the C3 position followed by cheletropic loss of CO from the intermediary 2-azanorbornene (path C reaction). The validity of path C was proved by isolation of the 2-azanorbornenes (21 and 22) formed by thermolysis of the 7-vinyl-4-acetoxy imidate (20).

  1-芳基-5-乙氧羧基-2-氮杂双环[3.2.0]庚烷-3,4-二酮的7-乙烯基衍生物的热分解导致了两种不同类型的骨架重排，具体取决于7-乙烯基基团的立体化学。外异构体（2）通过C1-C7键向乙烯基基团的1,3转移反应生成了氢吲哚（4）（路径A反应），而内异构体（3）则通过科普重排反应生成了7-氮杂双环[4.2.1]非烷（5）（路径B反应）。相应的氮杂亚胺的热分解产物也取决于7-乙烯基基团的立体化学。内异构体（13）生成了科普产物（12），而外异构体（14）则生成了二氢吡啶酮（16），其产生是通过C1-C7键向C3位置的1,3转移，并随后从中间体2-氮杂诺本二烯中脱去CO（路径C反应）。通过分离由7-乙烯基-4-乙酰氧基氮杂亚胺（20）热分解形成的2-氮杂诺本二烯（21和22），证明了路径C的有效性。
• Sano, Takehiro; Horiguchi, Yoshie; Tsuda, Yoshisuke, Heterocycles, 1981, vol. 16, # 3, p. 359 - 362
  作者：Sano, Takehiro、Horiguchi, Yoshie、Tsuda, Yoshisuke

  DOI：——

  日期：——
• Sano, Takehiro; Horiguchi, Yoshie; Kambe, Suetaka, Heterocycles, 1981, vol. 16, # 6, p. 893 - 896
  作者：Sano, Takehiro、Horiguchi, Yoshie、Kambe, Suetaka、Toda, Jun、Taga, Jun-ichi、Tsuda, Yoshisuke

  DOI：——

  日期：——
• Sano, Takehiro; Horiguchi, Yoshie; Tanaka, Kazuhiko, Chemical and pharmaceutical bulletin, 1985, vol. 33, # 12, p. 5197 - 5201
  作者：Sano, Takehiro、Horiguchi, Yoshie、Tanaka, Kazuhiko、Tsuda, Yoshisuke

  DOI：——

  日期：——