3-Diazo-4-penten-2-one | 132524-93-7

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 3-Diazo-4-penten-2-one
• 英文别名: 3-Diazopent-4-en-2-one
• CAS: 132524-93-7
• 化学式: C₅H₆N₂O
• 分子量: 110.115
• InChiKey: QSSMZOIDMNDOQB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  19.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-Diazo-4-penten-2-one 在 RhCl(PPh₃)3 rhodium(II) octanoate 、 四丁基氟化铵 、 氢气 、 sodium cyanoborohydride 作用下， 以 四氢呋喃 、 乙醇 、 水 、 甲苯 、 乙腈 为溶剂， 25.0 ℃ 、310.27 kPa 条件下， 反应 36.25h， 生成 1-(8-甲基-8-氮杂双环[3.2.1]辛-2-烯-2-基)乙酮
  参考文献：
  名称：

  Synthesis of (.+-.)-ferruginine and (.+-.)-anhydroecgonine methyl-ester by a tandem cyclopropanation/Cope rearrangement

  摘要：

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethanes in the presence of N-(alkoxycarbonyl)pyrroles led to the synthesis of 8-azabicyclo[3.2.1]octa-2,6-dienes. The vinylcarbenoids generated from vinyldiazomethanes with a single electron-withdrawing group exhibited competing reactivity at the vinyl terminus in addition to the carbenoid site. Good regiocontrol was possible, however, by appropriate choice of catalyst and solvent. The practicality of this new approach to tropane alkaloids was demonstrated through short syntheses of (+/-)-ferruginine, (+/-)-anhydroecgonine methyl ester, and the lower homologue of (+/-)-anatoxin a.

  DOI：

  10.1021/jo00019a044
• 作为产物：
  描述：

  戊-3-烯-2-酮 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 生成 3-Diazo-4-penten-2-one
  参考文献：
  名称：

  单取代铑稳定的乙烯基类胡萝卜素的反常反应性

  摘要：

  与具有两个吸电子基团的铑（II）稳定的乙烯基类化合物相比，相关的单取代乙烯基类化合物在类胡萝卜素中心或乙烯基位置表现出反应性。反应部位可通过适当的催化剂和溶剂控制，从而通过串联环丙烷化/ Cope重排序列有效合成双环系统。

  DOI：

  10.1016/s0040-4039(00)97047-3

文献信息

• Direct Access to β-Oxodiazo Compounds by Copper(II)-Catalyzed Oxidative Rearrangement of Stabilized Vinyl Diazo Derivatives
  作者：José Barluenga、Giacomo Lonzi、Lorena Riesgo、Miguel Tomás、Luis A. López

  DOI：10.1021/ja208965b

  日期：2011.11.16

  The copper(II)-catalyzed reaction of alkenyldiazo compounds with iodosylbenzene leading to β-oxodiazo derivatives is reported. This process occurs via an unprecedented 1,2-shift of the diazoacetate function. A selection of the synthetic applications of a representative member of this new class of functionalized diazo derivatives in the regioselective synthesis of substituted 1,4-dicarbonyl compounds

  报道了烯基重氮化合物与碘代苯在铜 (II) 催化下反应生成 β-氧代重氮衍生物。这个过程是通过重氮乙酸酯功能前所未有的 1,2-转变发生的。还报道了这类新型官能化重氮衍生物的代表性成员在取代 1,4-二羰基化合物的区域选择性合成中的合成应用选择。
• Synthesis of 2.beta.-Acyl-3.beta.-aryl-8-azabicyclo[3.2.1]octanes and Their Binding Affinities at Dopamine and Serotonin Transport Sites in Rat Striatum and Frontal Cortex
  作者：Huw M. L. Davies、Elie Saikali、Nicholas J. S. Huby、Vernon J. Gilliatt、Julius J. Matasi、Tammy Sexton、Steven R. Childers

  DOI：10.1021/jm00035a005

  日期：1994.4

  A novel entry to tropane analogs of cocaine was developed on the basis of the reaction of rhodium-stabilized vinylcarbenoids with pyrroles. These analogs were tested:in binding to dopamine and serotonin (5-HT) transporters in:membranes from rat striatum and frontal cortex. In all the analogs, the aryl group at the 3-position was directly bound to the tropane ring (as in WIN-35,428), and methyl or ethyl ketone moieties were present at the a-position instead of the typical ester group. The series of analogs containing a 2-naphthyl group at the 3-position were most potent, with K-i values < 1 nM in binding to both dopamine and 5-HT transporters. Although the unsubstituted 2-naphthyl analog was nonselective at dopamine and 5-HT transport sites, other compounds:were selective for either site. In general, compounds with relatively small substituents on the aromatic moiety (such as p-methyl or p-fluoro) were relatively selective for the dopamine transporters, while a p-isopropylphenyl derivative was selective:for the 5-HT transport sites. This latter compound represents the first N-methyltropane derivative specific for 5-HT transporters. Resolution of two of the most significant analogs was achieved by HPLC on a chiral stationary phase; the active enantiomer of a 2-naphthyl analog exhibited K-i values of <0.1 nM at both dopamine and 5-HT transporter sites.
• DAVIES, HUW M. L.;SAIKALI, ELIE;CLARK, JEFFREY T.;CHEE, EDWIN H., TETRAHEDRON LETT., 31,(1990) N4, C. 6299-6302
  作者：DAVIES, HUW M. L.、SAIKALI, ELIE、CLARK, JEFFREY T.、CHEE, EDWIN H.

  DOI：——

  日期：——