4-diazo-5-hexen-3-one | 155930-86-2

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: 4-diazo-5-hexen-3-one
• 英文别名: 4-Diazohex-5-en-3-one；4-diazohex-5-en-3-one
• CAS: 155930-86-2
• 化学式: C₆H₈N₂O
• 分子量: 124.142
• InChiKey: FVKBIPPSMFKRMX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.33
• 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：

  4-diazo-5-hexen-3-one 在 rhodium(II) octanoate 、 (PPh₃)RhCl 、 氢气 、 sodium cyanoborohydride 、 三氟乙酸 作用下， 生成 8-methyl-2-propanoyl-8-azabicyclo<3.2.1>oct-2-ene
  参考文献：
  名称：

  Synthesis and monoamine transporter affinity of 3β-(4-(2-pyrrolyl)phenyl)-8-azabicyclo[3.2.1]octanes and 3β-(5-Indolyl)-8-azabicyclo[3.2.1]octanes

  摘要：

  3 beta-(5-Indolyl)-8-azabicyclo[3.2.1]octanes display potent binding affinity for both the dopamine and serotonin transporters, while certain 3 beta-(4-(2-pyrrolyl)phenyl)-8-azabicyclo[3.2.1]octanes selectively bind to the serotonin transporter. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0960-894x(00)00701-0
• 作为产物：
  描述：

  5-己烯-3-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， 以 乙腈 为溶剂， 以68%的产率得到4-diazo-5-hexen-3-one
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1021/jm00035a005

文献信息

• Rhodium Carboxylate Catalyzed Decomposition of Vinyldiazoacetates in the Presence of Heterodienes:  Enantioselective Synthesis of the 6-Azabicyclo[3.2.2]nonane and 6-Azabicyclo[3.2.2]nonanone Ring Systems
  作者：Huw M. L. Davies、L. Mark Hodges

  DOI：10.1021/jo025697g

  日期：2002.8.1

  catalyzed decomposition of vinyldiazoacetates in the presence of N-phenoxycarbonyl protected 1,2-dihydropyridines or 1-methyl-2-pyridones is a direct method for the construction of the 6-azabicyclo[3.2.2]nonane ring system. The [3 + 4] cycloaddition occurs by a tandem cyclopropanation/Cope rearrangement. Asymmetric induction is possible in these transformations either by using (S)-lactate methyl ester

  在N-苯氧羰基保护的1，2-二氢吡啶或1-甲基-2-吡啶酮的存在下，四羧酸二丙酯催化的重氮乙酸乙烯酯的分解是构建6-氮杂双环[3.2.2]壬烷环系统的直接方法。[3 + 4]环加成反应是通过串联环丙烷化/ Cope重排而发生的。通过使用（S）-乳酸甲酯作为手性助剂或四脯氨酸二吡啶鎓作为手性催化剂，在这些转化中可能发生不对称诱导。
• Rhodium(II)-catalyzed decomposition of vinyldiazomethanes in the presence of 1,2-dihydropyridines: Synthesis of the 6-azabicyclo[3.2.2]nonane nucleus
  作者：Huw M.L. Davies、L.Mark Hodges、Craig T. Thornley

  DOI：10.1016/s0040-4039(98)00412-2

  日期：1998.4

  6-azabicyclo[3.2.2]nonadienes was synthesized via rhodium(II)-catalyzed decomposition of vinyldiazomethanes in the presence of substituted dihydropyridines. The regioselectivity of the reaction was shown to be highly dependent on the steric bulk of the catalyst as well as the structure of the vinyldiazomethane. Each regioisomer was elaborated into higher homologs of ferruginine (1, 2).

  在取代的二氢吡啶存在下，通过铑（II）催化乙烯基重氮甲烷的分解，合成了一系列官能化的6-氮杂双环[3.2.2]壬二烯。已表明反应的区域选择性高度取决于催化剂的空间体积以及乙烯基重氮甲烷的结构。每个区域异构体都被精制为较高的铁精氨酸同源物（1、2）。
• Diastereoselective Kinetic Protonation of Exocyclic Enolates Derived from Bicyclic Ketones:  Control of Stereochemistry Mediated by Bridging Heteroatoms
  作者：Huw M. L. Davies、L. Mark Hodges、Timothy M. Gregg

  DOI：10.1021/jo0158940

  日期：2001.11.1
• 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.
• Synthesis and monoamine transporter affinity of 3β-(4-(2-pyrrolyl)phenyl)-8-azabicyclo[3.2.1]octanes and 3β-(5-Indolyl)-8-azabicyclo[3.2.1]octanes
  作者：Huw M.L Davies、Pingda Ren、Norman Kong、Tammy Sexton、Steven R Childers

  DOI：10.1016/s0960-894x(00)00701-0

  日期：2001.2

  3 beta-(5-Indolyl)-8-azabicyclo[3.2.1]octanes display potent binding affinity for both the dopamine and serotonin transporters, while certain 3 beta-(4-(2-pyrrolyl)phenyl)-8-azabicyclo[3.2.1]octanes selectively bind to the serotonin transporter. (C) 2001 Elsevier Science Ltd. All rights reserved.