2-methylene 3-oxo methyl cyclopentane carboxylate | 72525-99-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: 2-methylene 3-oxo methyl cyclopentane carboxylate
• 英文别名: (+/-)-sarkomycin methyl ester；sarkomycin methyl ester；3-Methoxycarbonyl-2-methylidene cyclopentanone；3-methoxycarbonyl-2-methylidenecyclopentanone；methyl 2-methylidene-3-oxocyclopentane-1-carboxylate
• CAS: 72525-99-6
• 化学式: C₈H₁₀O₃
• 分子量: 154.166
• InChiKey: MZIVFPBRQACWDG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-methylene 3-oxo methyl cyclopentane carboxylate 在 acid 作用下， 以33%的产率得到sarkomycin
  参考文献：
  名称：

  到沙霉素的简单途径

  摘要：

  Synthese de la sarkomycine soit a partir d'un spiro [cyclopentene-1:9'-ethano-9',10' anthracene] soit a partir d'un adduit itaconate-anthracene

  DOI：

  10.1021/ja00329a038
• 作为产物：
  描述：

  4-<2-(methoxycarbonyl)ethyl>tetrahydrofura-2-one 在 chromium(VI) oxide 、 盐酸 、 potassium tert-butylate 、 potassium carbonate 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 42.8h， 生成 2-methylene 3-oxo methyl cyclopentane carboxylate
  参考文献：
  名称：

  Efficient enantioselective synthesis of the antitumor agent sarkomycin

  摘要：

  DOI：

  10.1021/jo01292a053

文献信息

• Syntheses of nitrile and methyl ester corresponding to (dl)-sarkomycin and of related compounds
  作者：Jacques Froissant、Joëlle Vidal、Eryka Guibé-Jampel、Francois Huet

  DOI：10.1016/s0040-4020(01)89959-2

  日期：1987.1

  3-trimethylsiloxy 2-cycloalkene carbonitriles. Their alkylation with chloromethyl phenyl sulfide followed by oxone oxidation to sulfones and sulfinic acid elimination on basic alumina led to α-methylene carbonyl compounds. Obtention of the ester involved acetalization of 3-oxo 2-phenylthiomethyl cyclopentane carbonitrile, basic hydrolysis into acid, deacetalization, estenfication, oxidation and elimination of sulfinic

  腈和酯对应于（DL）-sarkomycin，6-和7-元环类似物腈，和3-甲基取代的腈制备。将氰基三甲基硅烷共轭添加到环状α-烯酮中，得到3-三甲基甲硅烷氧基2-环烯烃腈。它们用氯甲基苯硫醚进行烷基化，然后将酮氧化成砜，然后在碱性氧化铝上消除亚磺酸，生成α-亚甲基羰基化合物。获得该酯涉及3-氧代2-苯基硫代甲基环戊烷腈的缩醛化，碱性水解成酸，脱缩醛化，酯化，氧化和消除亚磺酸。
• The efficient consecutive β-carboxylation and α-alkylation of cyclic α,β-enones; a new route to sarkomycin
  作者：Junzo Otera、Yoshihisa Niibo、Hiroshi Aikawa

  DOI：10.1016/s0040-4039(00)96066-0

  日期：1987.1

  introduction of a carboxy group equivalent and an alkyl group at the respective β- and α-positions of cyclic enones has been achieved through a 1,4-addition reaction of [methoxy(phenylthio)(trimethylsilyl)methyl] lithium followed by direct trapping of the resulting enolate with alkyl halides. The present method proved to be applicable to a simple synthesis of sarkomycin.

  通过[甲氧基（苯硫基）（三甲基甲硅烷基）甲基]锂的1,4-加成反应，随后在环烯酮的相应β-和α-位置上依次一键式引入羧基当量和烷基通过用卤代烷直接捕集所得的烯醇化物。经证明，本方法适用于沙克霉素的简单合成。
• Total Synthesis of Racemic and Optically Active Sarkomycin
  作者：Marian Mikołajczyk、Remigiusz Żurawiński、Piotr Kiełbasiński、Michał W. Wieczorek、Jarosław Błaszczyk、Wiesław R. Majzner

  DOI：10.1055/s-1997-1193

  日期：1997.3

  trans-3-Carboxy-2-diethoxyphosphorylcyclopentanone (11), a key precursor of sarkomycin 1, has been synthesized in the rhodium(II) acetate promoted cyclization of diethyl 1-diazo-2-oxohept-6-enephosphonate (9), followed by transformation of the 3-vinyl moiety into the 3-carboxylic group. Racemic 11 has been resolved into enantiomers via diastereoisomeric enamine-type derivatives 13 resulting from its reaction with (-)-(S)-1-(1-naphthyl)ethylamine. The structure and absolute configuration of 13 have been determined by X-ray crystal structure analysis. The enantiomerically enriched (up to 77.6% ee) acid 11 has also been obtained in the enzyme-promoted hydrolysis of racemic 2-diethyoxyphosphoryl-3-methoxycarbonylcyclopentanone (12). The Horner-Wittig reaction of 11 with gaseous formaldehyde has been applied to introduce the exocyclic α-methylene moiety into the cyclopentanone system and thus to complete the synthesis of the racemate and, for the first time, each enantiomer of sarkomycin 1. A phenomenon of enantiomer self-discrimination has been observed in 31PNMR spectra of the nonracemic acid 11 and explained in terms of the formation of the hydrogen bonded homo- and hetero-dimers. The existence of dimeric structures has been confirmed by X-ray analysis of the structurally closely related trans-3-carboxy-2-diphenylphosphinoyl-cyclopentanone (16).

  反式-3-羧基-2-二乙氧基磷酰环戊酮（11）是沙考霉素 1 的关键前体，它是在 1-重氮-2-氧代庚基-6-烯基膦酸二乙酯（9）的乙酸铑（II）促进环化反应中合成的，随后 3-乙烯基转变为 3-羧基。外消旋 11 与(-)-(S)-1-(1-萘基)乙胺反应生成的非对映异构体烯胺类衍生物 13 将外消旋 11 分解成对映体。通过 X 射线晶体结构分析确定了 13 的结构和绝对构型。外消旋 2-二乙氧基磷酰-3-甲氧羰基环戊酮（12）在酶促水解过程中也得到了对映体富集（ee高达 77.6%）的酸 11。11 与气态甲醛的霍纳-维蒂希反应被用于将外环δ-亚甲基引入环戊酮体系，从而完成了外消旋体的合成，并首次合成了沙可霉素 1 的各对映体。通过对结构上密切相关的反式-3-羧基-2-二苯基膦酰基环戊酮（16）进行 X 射线分析，证实了二聚体结构的存在。
• NOVEL COMPOUND HAVING EFFECT OF PROMOTING NEURON DIFFERENTIATION
  申请人：Nippon Kayaku Kabushiki Kaisha

  公开号：EP0999204A1

  公开（公告）日：2000-05-10

  A novel cystacycline derivative provided according to the present invention has a novel neuron differentiation promoting activity and is thus useful as a medicament for the treatment of central and peripheral nervous system disorders and the like.

  根据本发明提供的一种新型胱氨酸衍生物具有促进神经元分化的新型活性，因此可用作治疗中枢和周围神经系统疾病等的药物。
• Use of alumina for elimination of sulfinic acid from β-aryl- and β-alkylsulfonyl carbonyl compounds.
  作者：Joëlle Vidal、Francois Huet

  DOI：10.1016/s0040-4039(00)83866-6

  日期：1986.1