2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane | 103960-21-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane
• 英文别名: 1-Diazo-3-(2-methyl-1,3-dioxolan-2-yl)propan-2-one
• CAS: 103960-21-0
• 化学式: C₇H₁₀N₂O₃
• 分子量: 170.168
• InChiKey: YLVVNJCQMRUWAI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.71
• 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-(3'-diazo-2'-oxopropyl)-2-methyldioxolane 以68%的产率得到
  参考文献：
  名称：

  ROSKAMP E. J.; JOHNSON C. R., J. AMER. CHEM. SOC., 108,(1986) N 19, 6062-6063

  摘要：

  DOI：
• 作为产物：
  描述：

  苹果酯 在 盐酸 、 sodium hydroxide 、 三乙胺 、 氯甲酸甲酯 作用下， 生成 2-(3'-diazo-2'-oxopropyl)-2-methyldioxolane
  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

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。
• Catalysis of chlorosilane on the ring-expansion of cyclic acetals bearing a carbene precursor. Lewis acid–base effect on the oxonium ylide intermediate
  作者：Takashi Mori、Akira Oku

  DOI：10.1039/a903928g

  日期：——

  Rhodium catalyzed (1–0.1 mol%) decomposition of 2-(3-diazo-2-oxopropyl)-2-methyldioxolane 1a or 2-(3-diazo-1-methyl-2-oxopropyl)-2-methyldioxolane 1b in the presence of a catalytic amount of TMSCl (10 mol%), yielded 4,7-dioxocane 3a (91%) or 3b (49%), whereas similar reaction in the absence of TMSCl caused 1,2-rearrangement to give bicyclobutanones 2a or 2b, respectively; Lewis acid-base catalysis by TMSCl of the ring-expansion of a bicyclooxonium ylide intermediate is revealed.

  在催化量的 TMSCl（10 mol%）存在下，铑催化（1-0.1 mol%）2-(3-重氮-2-氧代丙基)-2-甲基二氧戊环 1a 或 2-(3-重氮-1-甲基-2-氧代丙基)-2-甲基二氧戊环 1b 的分解，分别生成 4,7-二氧代环己烷 3a（91%）或 3b（49%），而在没有 TMSCl 的情况下，类似的反应导致 1,2-重排，分别生成双环丁酮 2a 或 2b；TMSCl 对双环氧鎓亚胺中间体的环扩的刘易斯酸碱催化作用得以揭示。
• Aldol-type carbon bond formation of ethereal oxonium ylide
  作者：Yuichi Sawada、Takashi Mori、Akira Oku

  DOI：10.1039/b102248m

  日期：——

  The Rh(2)-catalyzed reaction of 2-(3-diazo-1,1-dimethyl-2-oxopropyl)-2-methyldioxolane (1b) with arylaldehyde in the presence of (Me)3SiCl and Ti(i-PrO)4 gave 2-aryl-(hydroxy)methyl-8,8-dimethyl-7-methylene-3,6-dioxocane-1-one (6) and 2-aryl(hydroxy)methyl-4-(2-chloroethoxy)-4,5,5-trimethyl-3-oxacyclopentanone (7); these are the first examples of C–C bond formation of ethereal oxonium ylide via enol silyl ether intermediates.

  8-二甲基-7-亚甲基-3,6-二氧杂环戊烷-1-酮 (6) 和 2-芳基（羟基）甲基-4-（2-氯乙氧基）-4,5,5-三甲基-3-氧杂环戊酮 (7)；这些都是通过烯醇硅醚中间体形成乙氧基羰基键的第一个实例。
• Generation and rearrangements of oxonium ylides
  作者：Eric J. Roskamp、Carl R. Johnson

  DOI：10.1021/ja00279a077

  日期：1986.9