3-diazo-4-hydroxy-4-phenyl-butan-2-one | 39910-61-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 3-diazo-4-hydroxy-4-phenyl-butan-2-one
• 英文别名: 3-Diazo-4-hydroxy-4-phenylbutan-2-one；3-diazo-4-hydroxy-4-phenylbutan-2-one
• CAS: 39910-61-7
• 化学式: C₁₀H₁₀N₂O₂
• 分子量: 190.202
• InChiKey: LRCPOHNSAWHDBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  39.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3-diazo-4-hydroxy-4-phenyl-butan-2-one 在 rhodium(II) acetate dimer 作用下， 以 乙二醇二甲醚 为溶剂， 反应 0.17h， 以90%的产率得到1-苯基-1,3-丁二酮
  参考文献：
  名称：

  一种由醛制备β-二酮的改进的两步法及其在β-金刚烷酮合成中的应用

  摘要：

  通过将醛与1-重氮-1-硫代丙酮缩合而制得的α-重氮-β-羟基酮可通过暴露于乙酸铑（II）而有效地转化为相应的β-二酮。该序列被应用于新合成的β-金刚烷酮（10）。

  DOI：

  10.1039/p19810002566
• 作为产物：
  描述：

  3-diazo-4-phenyl-4-(triethylsilyloxy)-butan-2-one 在 triethylamine tris(hydrogen fluoride) 作用下， 以 乙醚 为溶剂， 反应 3.0h， 以100%的产率得到3-diazo-4-hydroxy-4-phenyl-butan-2-one
  参考文献：
  名称：

  TBAF-Triggered Aldol-Type Addition of α-Triethylsilyl-α-diazoacetone

  摘要：

  Aldol-type addition of alpha-triethylsilyl-alpha-diazoacetone was achieved under nucleophilic activation by tetrabutylammonium fluoride (TBAF). The use of a semi-stoichiometric amount of TBAF (protocol P1) provided the corresponding beta-hydroxy-alpha-diazoacetone as the sole product. Alternatively, the use of a catalytic amount of TBAF led to a mixture of beta-hydroxy- and beta-silyloxy-alpha-diazoacetone products, which was cleanly desilylated with Et3N center dot 3HF (protocol P2). The weakly basic conditions employed tolerate a wide range of substrates and constitute a high-yielding, convenient complementary procedure to the low-temperature LDA-promoted aldol-type addition of diazoacetone.

  DOI：

  10.1021/acs.joc.5b01554

文献信息

• DBU-promoted condensation of acyldiazomethanes to aldehydes and imines under catalytic conditions
  作者：Nan Jiang、Jianbo Wang

  DOI：10.1016/s0040-4039(01)02375-9

  日期：2002.2

  The condensation of acyldiazomethanes to aldehydes and imines can be promoted with catalytic amount of DBU. The condensation gives β-hydroxy α-diazo carbonyl compounds or β-amino α-diazo carbonyl compounds in high yields.

  可以用催化量的DBU促进酰基重氮甲烷与醛和亚胺的缩合。缩合以高收率得到β-羟基α-重氮羰基化合物或β-氨基α-重氮羰基化合物。
• Synthesis of Vinylcyclopropanes, Cyclopropyl Vinyl Ketones, and 3-Pyrazolyl Vinyl Ketones from 1-Diazo-3-trimethylsilylpropanone
  作者：Otohiko Tsuge、Shuji Kanemasa、Toshiro Suzuki、Koyo Matsuda

  DOI：10.1246/bcsj.59.2851

  日期：1986.9

  cupric acetylacetonate (Cu(acac)2) affords cyclopropyl trimethylsilylmethyl ketones. One-flask procedure for the formation of these silylated ketones and subsequent treatment with organometallics or with lithium diisopropylamide (LDA) and then carbonyl compounds gives a variety of vinylcyclopropanes or cyclopropyl vinyl ketones in good yields, respectively. Cycloaddition of 1-diazo-3-trimethylsilylpropanone

  在乙酰丙酮酸铜 (Cu(acac)2) 存在下，1-重氮-3-三甲基甲硅烷基丙酮与烯烃反应得到环丙基三甲基甲硅烷基甲基酮。用于形成这些甲硅烷基化酮并随后用有机金属化合物或二异丙基氨基锂 (LDA) 和羰基化合物处理的单烧瓶程序分别以良好的产率得到各种乙烯基环丙烷或环丙基乙烯基酮。1-重氮-3-三甲基甲硅烷基丙酮与乙炔的环加成以及环加合物侧链上类似的碳-碳键形成导致3-吡唑基乙烯基酮。
• 1,2-Migration in Rhodium(II) Carbene Transfer Reaction:  Remarkable Steric Effect on Migratory Aptitude
  作者：Fengping Xiao、Jianbo Wang

  DOI：10.1021/jo0605391

  日期：2006.7.1

  been prepared in order to investigate the steric effect in 1,2-migration reaction of rhodium(II) carbene. Through the investigation on the diazo decomposition of these compounds with Rh2(OAc)4, it was found that the steric effect could dramatically influence the migratory aptitude. In many cases, the steric effect could override the inherent electronic effect of the substituent.

  为了研究铑（II）卡宾在1,2-迁移反应中的空间效应，已经制备了一系列带有不同取代基的重氮羰基化合物。通过对这些化合物与Rh 2（OAc）4的重氮分解研究，发现空间效应可显着影响迁移能力。在许多情况下，空间效应可能会取代取代基的固有电子效应。
• Advances in the TBAF-induced aldol-type addition of α-trialkylsilyl-α-diazoacetones: TIPS versus TES
  作者：Imen Abid、Sigrid Gavelle、Anne-Caroline Chany、Frédéric Legros、Pascal Gosselin、Souhir Abid、Gilles Dujardin、Catherine Gaulon-Nourry

  DOI：10.1016/j.crci.2016.12.005

  日期：2017.6

  Résumé α-Triisopropylsilyl-α-diazoacetone (TIPS-diazoacetone) underwent high-yielding “diazo-side” Mukaiyama aldol-type addition with a range of aryl and alkyl aldehydes when subjected to stoichiometric amount of tetrabutylammonium fluoride at −16 °C, in Et2O. Robustness of the TIPS group makes TIPS-diazoacetone a stable surrogate for α-triethylsilyl-α-diazoacetone, on which generation of the corresponding carbanion can still be efficiently achieved under nucleophilic, weakly basic and practical conditions. These results highlight the synthetic potential that can be expected from TIPS-diazoacetone, promising building block for the convergent elaboration of highly functionalised versatile diazocarbonyl compounds.

  摘要 α-三异丙基硅基-α-二氟乙酮（TIPS-diazoacetone）在-16°C下，使用等当量的四丁基氟铵和醚溶剂进行“二氟侧”Mukaiyama醇醛型加成，与多种芳基和烷基醛发生了高产率的反应。TIPS基团的稳健性使得TIPS-diazoacetone成为α-三乙基硅基-α-二氟乙酮的稳定替代物，相应的负离子在亲 nucleophilic、弱碱和实用条件下仍然可以高效产生。这些结果突显了TIPS-diazoacetone所期待的合成潜力，预示着它是合成高度功能化、多用途二氟羰基化合物的有前景的构建单元。
• Unusual reaction of β-hydroxy α-diazo carbonyl compounds with TsNHNCHCOCl/Et3N
  作者：Weifeng Shi、Bo Zhang、Binge Liu、Feng Xu、Fengping Xiao、Jian Zhang、Shiwei Zhang、Jianbo Wang

  DOI：10.1016/j.tetlet.2004.04.037

  日期：2004.5

  The reaction of β-hydroxy α-diazo carbonyl compounds with TsNHNCHCOCl/Et3N gave β-(p-tolylsulfonyl) α,β-unsaturated carbonyl compounds or β-(p-tolylsulfonyl) α-diazo esters. The reaction mechanism is discussed.

  β-羟基α-重氮羰基化合物与TsNHNCHCOCl/ Et 3 N反应得到β-​​（对甲苯磺酰基）α，β-不饱和羰基化合物或β-（对甲苯磺酰基）α-重氮酯。讨论了反应机理。