2-(4-diazo-2-oxobutyl)-2-methyldioxolane | 188406-86-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(4-diazo-2-oxobutyl)-2-methyldioxolane
• 英文别名: 1-diazo-4-(2-methyl-1,3-dioxolan-2-yl)butan-2-one；1-Diazo-4-(2-methyl-1,3-dioxolan-2-yl)butan-2-one
• CAS: 188406-86-2
• 化学式: C₈H₁₂N₂O₃
• 分子量: 184.195
• InChiKey: XHBFPONWEDIWJH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  37.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-(4-diazo-2-oxobutyl)-2-methyldioxolane 在 dirhodium tetraacetate 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 生成 4-methylene-5,8-dioxonan-1-one
  参考文献：
  名称：

  Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides

  摘要：

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.

  DOI：

  10.1021/jo961844x
• 作为产物：
  描述：

  2-甲基-1,3-二氧戊环-2-丙酸 在 草酰氯 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 24.0h， 生成 2-(4-diazo-2-oxobutyl)-2-methyldioxolane
  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

• Carbon−Carbon Bond Formation Reaction of Ethereal Oxonium Ylides via Metal−Enolate Intermediates
  作者：Yuichi Sawada、Takashi Mori、Akira Oku

  DOI：10.1021/jo035272+

  日期：2003.12.1

  First, the carbon-carbon (C-C) bond-forming reaction of aldehydes with bicyclo[m.n.0]-1-oxonium ylides was studied as the ylide was transiently formed in the Rh(II)-catalyzed reaction of a nonenolizable diazoketone, namely, 2-(3-diazo-1,1-dimethyl-2-oxopropyl)-2-methyldioxolane (1). The reaction of 1 with benzaldehyde in the presence of ClTi(Oi-Pr)3 gave the three-carbon, ring-enlarged, and C-C-bonded

  首先，研究了醛与双环[mn0] -1-氧鎓鎓盐形成碳-碳（CC）键的反应，因为在不可烯化的重氮酮的Rh（II）催化反应中瞬时形成了内鎓盐，即2 -（3-重氮-1,1-二甲基-2-氧丙基）-2-甲基二氧戊环（1）。1在ClTi（Oi-Pr）3的存在下与苯甲醛的反应生成了三碳，环扩大且CC键合的产物2a（53％）。其次，在相似的催化条件下研究了在α位不带甲基取代基的可烯丙基重氮酮5，并且当钛化合物ClTi（Oi-Pr）形成环扩大和CC键合产物19a和20a（87％）。使用3或Ti（Oi-Pr）4。带有环状乙缩醛环和比5长的束缚链的重氮酮27、29和31的相似反应得到CC键合产物28（74％），30（8％），分别为32和33（占总48％），尽管28和30具有螺双缩醛结构。因此，通过使用合适的路易斯酸，例如ClTi（Oi-Pr）3，迄今仍未弄清醚羰基醚与羰基亲电试剂的CC键形成。
• Three- and Four-Carbon Elongating Ring Expansion of Cyclic Acetals to Medium-Sized Dioxacycloalkenones. Use of the Intramolecular Formation of Oxonium Ylides
  作者：Akira Oku、Nobuhito Murai、Julia Baird

  DOI：10.1021/jo961844x

  日期：1997.4.1

  The Rh(II)-catalyzed reaction of 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane (1) in the presence of a protic nucleophile (NuH) such as AcOH resulted in effective ring enlargement to give the 8-membered 3-acetoxydioxocanone 4a (41%) and dioxocan-2-en-1-one 3 (46%). Similar treatment of 2-(4'-diazo-3'-oxobutyl)-2-methyldioxolane (9) with AcOH gave 4-acetoxydioxonanone 10 (67%), which was readily hydrolyzed on silica gel to a tautomeric mixture of hydrolysis products 16a and 16b (total yield 46%). In contrast, similar treatment of 2-(5'-diazo-4'-oxopentyl)-2-methyldioxolane (19) gave 2,5-dioxa-1-methyldecalin-7-one (20, 24%), and the yield increased to 61% in the absence of AcOH, by Stevens rearrangement. The reaction of 1,3-dioxane homologues 26 and 31 gave similar results. All of these reactions can be explained in terms of the intermediacy of bicyclooxonium ylides, which undergo either a Stevens rearrangement or, after protonation by a NuH, ring enlargement through release of the strain of the bicyclic ylides. Evidence of the reversible formation of oxonium ylides is also provided.
• Trimethylsilyldiazomethane as a Versatile Stitching Agent for the Introduction of Aziridines into Functionalized Organic Molecules
  作者：Hong Ren、William D. Wulff

  DOI：10.1021/ol102064b

  日期：2010.11.5

  A highly enantioselective route for the introduction of aziridines into functionalized organic molecules was developed via a tandem acylation and aziridination of TMSCHN2.

  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。