5-Bromo-1-diazopentan-2-one | 146580-95-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-Bromo-1-diazopentan-2-one
• 英文别名: 5-bromo-1-diazo-2-pentanone
• CAS: 146580-95-2
• 化学式: C₅H₇BrN₂O
• 分子量: 191.027
• InChiKey: VXVNFCAQPUGBDQ-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：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  5-Bromo-1-diazopentan-2-one 在 potassium fluoride 、 三正丁基氢锡 、 反式-二叔丁基连二次硝酸酯 作用下， 生成 5-溴-2-戊酮
  参考文献：
  名称：

  Radical addition to carbenoids. Chain reactions of α-diazo carbonyl compounds with triorganotin hydrides, tris(trimethylsilyl)silane and allyltributylstannane

  摘要：

  alpha-Diazo ketones RC(O)CH=N-2 react with tributyltin hydride at 60 degrees C in benzene to give the corresponding alpha-stannyl ketones RC(O)CH(2)SnBu(3), which exist in equilibrium with the stannyl enol ether tautomers R(Bu(3)SnO)C=CH2. The reactions are initiated by di-tert-butyl hyponitrite and follow a free-radical chain mechanism, Triphenyltin hydride and tris(trimethylsilyl)silane [(TMS)(3)SiH] react similarly, the latter to yield the alpha-silyl ketone RC(O)CH2Si(TMS)(3) which does not isomerise to the more stable silyl enol ether R[(TMS)(3)SiO]C=CH2 under the reaction conditions. This result indicates that TMS(3)Si reacts at the alpha-carbon atom of the alpha-diazo ketone to give R(CO)CHSiTMS(3), probably via an initial diazenyl radical adduct; triorganotin radicals are assumed to react in the same way, When the group R in the alpha-diazo ketone is but-3-enyl, the intermediate alpha-metalloalkyl radical undergoes 5-exo-cyclisation. Aliyltributylstannane reacts with a-diazo ketones and with ethyl alpha-diazoacetate in refluxing benzene, in the presence of 2,2'-azo(2-methylpropionitrile) as initiator, to give butenyl ketones RC(O)CH2CH2CH=CH2 and ethyl pent-4-enoate, respectively, after a hydrolytic work-up.

  DOI：

  10.1039/p19960000769
• 作为产物：
  描述：

  4-溴丁酰氯 、 三甲基硅烷化重氮甲烷 以 乙腈 为溶剂， 反应 24.0h， 生成 5-Bromo-1-diazopentan-2-one
  参考文献：
  名称：

  三甲基甲硅烷基重氮甲烷作为多功能缝线剂，用于将氮丙啶引入功能化有机分子中

  摘要：

  通过串联酰化和叠氮化TMSCHN 2开发了将氮丙啶引入功能化有机分子的高度对映选择性的途径。

  DOI：

  10.1021/ol102064b

文献信息

• Mechanism of Gold(I)-Catalyzed Rearrangements of Acetylenic Amine-<i>N</i>-Oxides: Computational Investigations Lead to a New Mechanism Confirmed by Experiment
  作者：Elizabeth L. Noey、Yingdong Luo、Liming Zhang、K. N. Houk

  DOI：10.1021/ja208860x

  日期：2012.1.18

  Quantum mechanical studies of the mechanism of gold-catalyzed rearrangements of acetylenic amine-N-oxides to piperidinones or azepanones have revealed a new mechanism involving a concerted heteroretroene reaction, formally a 1,5 hydrogen shift from the N-alkyl groups to the vinyl position of a gold-coordinated methyleneisoxazolidinium or methyleneoxazinanium. Density functional calculations (B3LYP

  金催化炔胺-N-氧化物重排为哌啶酮或氮杂环庚酮的机理的量子力学研究揭示了一种新的机制，涉及协调的杂对四烯反应，形式上是从 N-烷基到乙烯基位置的 1,5 个氢位移金配位的亚甲基异恶唑啉鎓或亚甲基恶嗪鎓。异戊二烯机制的密度泛函计算（B3LYP、B3LYP-D3）重现了实验区域选择性，并解释了为什么氢从较小的胺取代基转移。为支持所提出的机制，新的实验研究表明氢转移是协调一致的，并且金卡宾不作为反应中间体参与。
• A short, enantioselective synthesis of (−)-epilupinine from proline via a spirocyclic ammonium ylide
  作者：B.N. Naidu、F.G. West

  DOI：10.1016/s0040-4020(97)01037-5

  日期：1997.12

  quinolizidine 8b with high diastereoselectivity (19:1 8b/7b) and in surprisingly high enantiomeric excess (75%). The key step presumably occurs via spirocyclic ylide 6b, which undergoes [1,2]-shift with retention. Rearrangement product 8b was converted to (−)-epilupinine 2 via an efficient, 3-step sequence.

  重氮酮5B，在从脯氨酸苄酯一步可用，后行转化为喹8B具有高非对映选择性（19：1的8b / 7B）和令人惊奇的高对映体过量（75％）。关键步骤大概是通过螺环内酯6b发生的，螺环内含物经历[1,2]移位。重排产物8b通过有效的3步序列转化为（-）-癫痫碱2。
• A Novel, Stereoselective Silyl-Directed Stevens [1,2]-Shift of Ammonium Ylides
  作者：John A. Vanecko、F. G. West

  DOI：10.1021/ol025951r

  日期：2002.8.1

  "placeholder" during regioselective 1,2-migration with retention by the resulting spirocyclic ammonium ylide, and a hydroxyl surrogate for an eventual stereoselective Fleming-Tamao oxidation. This chemistry represents a novel use of the Stevens rearrangement and offers a short, enantioselective route to hydroxylated quinolizidines such as 3 from Boc-pyrrolidine.

  [反应：参见正文] 2-甲硅烷基吡咯烷的甲硅烷基基团起几个关键作用：除环氮外，在面部选择性类胡萝卜素中的立体化学控制元素，在区域选择性1,2-迁移过程中保留的立体化学“占位符”通过生成的螺环铵盐和羟基替代物进行最终的立体选择性弗莱明-塔莫氧化。该化学反应代表了史蒂文斯重排的一种新颖用途，并提供了一条短的，对映选择性的途径，使之与羟基化的喹oli嗪类似，例如来自Boc-吡咯烷的3。
• Cu(OTf)₂-Catalyzed Synthesis of 2,3-Disubstituted Indoles and 2,4,5-Trisubstituted Pyrroles from α-Diazoketones
  作者：B. V. Subba Reddy、M. Ramana Reddy、Y. Gopal Rao、J. S. Yadav、B. Sridhar

  DOI：10.1021/ol303206w

  日期：2013.2.1

  A novel method has been devised for the synthesis of 2,4,5-trisubstituted pyrrole derivatives through the coupling of alpha-diazoketones with beta-enaminoketones and esters using 10 mol % of Cu(OTf)(2). A wide range of 2,3-disubstituted indole derivatives were also prepared from alpha-diazoketones and 2-aminoaryl or alkyl ketones. The synthetic versatility of this approach has been exemplified In the formal synthesis of homofascaplysin C.
• New route to substituted piperidines via the Stevens [1,2]-shift of ammonium ylides
  作者：F. G. West、B. N. Naidu

  DOI：10.1021/ja00056a069

  日期：1993.2