1-Diazo-6-phenyl-2,6-hexadione | 122889-62-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-Diazo-6-phenyl-2,6-hexadione
• 英文别名: 1-diazo-6-phenylhexane-2,6-dione；1-diazo-6-phenyl-2,6-hexanedione；6-Diazo-1-phenylhexane-1,5-dione
• CAS: 122889-62-7
• 化学式: C₁₂H₁₂N₂O₂
• 分子量: 216.239
• InChiKey: KMNLLZOFXQJQGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  3,5-二叔丁基邻苯醌 、 1-Diazo-6-phenyl-2,6-hexadione 在 rhodium(II) acetate dimer 作用下， 以 甲苯 为溶剂， 反应 1.0h， 以37%的产率得到3,5-bis(1,1-dimethylethyl)-6'-phenylspiro[3,5-cyclohexadiene-1,8'-[7,9]dioxabicyclo[4.2.1]octane]-2,2'-dione
  参考文献：
  名称：

  羰基化物与1,2-二酮的1,3-偶极环加成反应：新型螺氧杂双环的合成

  摘要：

  羰基化物与各种邻醌的1，3-偶极环加成反应提供了高度氧化的螺氧杂双环。

  DOI：

  10.1016/s0040-4020(02)00387-3
• 作为产物：
  描述：

  重氮甲烷 、 4-苯甲酰基丁酸 在 草酰氯 作用下， 生成 1-Diazo-6-phenyl-2,6-hexadione
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation

  摘要：

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.

  DOI：

  10.1021/jo00010a019

文献信息

• Cycloaddition of Carbonyl Ylides to Isatins: Synthesis of Novel Spiro Oxindoles
  作者：Vijay Nair、K. C. Sheela、D. Sethumadhavan、S. Bindu、Nigam P. Rath、Günter K. Eigendorf

  DOI：10.1055/s-2001-10764

  日期：——

  Facile dipolar cycloaddition reactions of isatins with carbonyl ylides, generated by Rh2(OAc)4 catalyzed reaction of α-diazo ketones yielding novel spiro oxindole derivatives are described.

  介绍了异汀类与羰基酰化物的简便双极环加成反应，该反应由 Rh2(OAc)4 催化δ-重氮酮反应生成，可产生新型螺吲哚衍生物。
• Catalytic Enantioselective Tandem Carbonyl Ylide Formation/1,3-Dipolar Cycloaddition Reactions of α-Diazo Ketones with Aromatic Aldehydes using Dirhodium(II) Tetrakis[N-benzene-fused-phthaloyl-(S)-valinate]
  作者：Hideyuki Tsutsui、Naoyuki Shimada、Takumi Abe、Masahiro Anada、Makoto Nakajima、Seiichi Nakamura、Hisanori Nambu、Shunichi Hashimoto

  DOI：10.1002/adsc.200600591

  日期：2007.3.5

  example of the enantioselective intermolecular 1,3-dipolar cycloaddition of a chiral dirhodium(II) catalyst-associated carbonyl ylide with an aromatic aldehyde dipolarophile is described. The tandem carbonyl ylide formation/cycloaddition reactions of 1-diazo-5-aryl-2,5-pentanediones with aromatic aldehydes using dirhodium(II) tetrakis[N-benzene-fused-phthaloyl-(S)-valinate] as a catalyst provide exclusively

  描述了手性dirhodium（II）催化剂相关的羰基内酯与芳香醛双极性亲和剂的对映选择性分子间1,3-偶极环加成的第一个成功实例。以四（二）- [ N-苯-稠合-邻苯二甲酰-（S）-戊酸]为催化剂，提供了1-重氮-5-芳基-2,5-戊二酮与芳族醛的串联羰基内酯形成/环加成反应。仅在ex的92％ee内才有exo环加成物。
• Cyclic carbonyl ylide formation from the rhodium (II) acetate catalyzed reaction of 1-diazoalkanediones
  作者：Albert Padwa、Richard L. Chinn、Susan F. Hornbuckle、Lin Zhi

  DOI：10.1016/s0040-4039(00)95185-2

  日期：1989.1

  Treatment of 1-diazoalkanediones with rhodium (II) acetate results in cyclization of the intermediate rhodium carbenoid to give a cyclic carbonyl ylide which readily undergoes bimolecular dipolar cycloaddition with various dipolarophiles.

  用乙酸铑（II）处理1-重氮烷二酮导致中间体铑类胡萝卜素环化，得到环状羰基叶立德，其容易与各种偶极亲和剂进行双分子偶极环加成。
• Enantiocontrol in Tandem Carbonyl Ylide Formation and Intermolecular 1,3-Dipolar Cycloaddition of α-Diazo Ketones Mediated by Chiral Dirhodium(II) Carboxylate Catalyst
  作者：Shinji Kitagaki、Masahiro Anada、Osamu Kataoka、Kentaro Matsuno、Chisato Umeda、Nobuhide Watanabe、Shun-ichi Hashimoto

  DOI：10.1021/ja983748e

  日期：1999.2.1
• PADWA, ALBERT;CHINN, RICHARD L.;HORNBUCKLE, SUSAN F.;ZHI, LIN, TETRAHEDRON LETT., 30,(1989) N 3, C. 301-304
  作者：PADWA, ALBERT、CHINN, RICHARD L.、HORNBUCKLE, SUSAN F.、ZHI, LIN

  DOI：——

  日期：——