diethyl 2-((tetrahydro-2H-pyran-2-yl)methyl)malonate | 91976-73-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: diethyl 2-((tetrahydro-2H-pyran-2-yl)methyl)malonate
• 英文别名: tetrahydropyran-2-ylmethyl-malonic acid diethyl ester；Tetrahydropyran-2-ylmethyl-malonsaeure-diaethylester；diethyl 2-(tetrahydro-2H-pyran-2-ylmethyl)malonate；diethyl 2-(oxan-2-ylmethyl)propanedioate
• CAS: 91976-73-7
• 化学式: C₁₃H₂₂O₅
• 分子量: 258.315
• InChiKey: SFFOYTLZZSBNNI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  18
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  61.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  diethyl 2-((tetrahydro-2H-pyran-2-yl)methyl)malonate 在 N-甲基二环己基胺 、 palladium diacetate 、 sodium hydride 、 双(2-二苯基磷苯基)醚 作用下， 以 四氢呋喃 、 苯 为溶剂， 生成 diethyl 4-(iodomethyl)-6-oxaspiro[4.5]decane-2,2-dicarboxylate
  参考文献：
  名称：

  远程未活化 C(sp3)−H 位点上的钯催化原子转移自由基环化：杂化乙烯基钯自由基中间体的氢原子转移

  摘要：

  一种新型温和、可见光诱导的钯催化氢原子易位/原子转移自由基环化（HAT/ATRC）级联已经开发出来。该方案涉及先前未知的杂化乙烯基钯自由基中间体的 1,5-HAT 过程，从而产生碘甲基碳环和杂环结构。

  DOI：

  10.1002/anie.201712775
• 作为产物：
  描述：

  四氢吡喃-2-甲醇 在 sodium hydroxide 、 苯磺酰氯 、 苯 作用下， 生成 diethyl 2-((tetrahydro-2H-pyran-2-yl)methyl)malonate
  参考文献：
  名称：

  New 5:6-dihydro-benzo (c) cinnoline derivatives and a process for their preparation

  摘要：

  公开号：

  US02778829A1

文献信息

• Room Temperature Hydroalkylation of Electron-Deficient Olefins:  sp³ C−H Functionalization via a Lewis Acid-Catalyzed Intramolecular Redox Event
  作者：Stefan J. Pastine、Kevin M. McQuaid、Dalibor Sames

  DOI：10.1021/ja053337f

  日期：2005.9.1

  A practical method for the intramolecular hydroalkylation of electron-deficient olefins has been developed. The direct transformation of benzylic, tertiary, and sterically hindered secondary sp3 C-H bonds into C-C bonds under the action of a catalytic amount of a variety of Lewis acids is described. The mechanism of these transformations is proposed to involve a tandem hydride transfer/cyclization sequence.
• Room Temperature Intramolecular Hydro-O-alkylation of Aldehydes:  sp³ C−H Functionalization via a Lewis Acid Catalyzed Tandem 1,5-Hydride Transfer/Cyclization
  作者：Stefan J. Pastine、Dalibor Sames

  DOI：10.1021/ol0522283

  日期：2005.11.1

  The scope and limitations of intramolecular hydro-O-alkylation of aldehyde substrates leading to spiroketals and bicyclic ketals and aminals is reported. The direct transformation of tertiary and sterically hindered secondary sp(3) C-H bonds into C-O bonds under the action of a catalytic amount of a variety of Lewis acids is described. The mechanism of these transformations is proposed to involve a tandem hydride transfer/cyclization sequence.
• Use of the Nonionic Superbase P(MeNCH₂CH₂)₃N in the Selective Monoalkylation of Active-Methylene Compounds
  作者：Subramaniam Arumugam、Dale McLeod、John G. Verkade

  DOI：10.1021/jo972350i

  日期：1998.5.1

  The symmetric active-methylene compounds CH2(CO2Et)(2) and CH2[C(O)Me](2) are selectively monoalkylated in the presence of 1.1 equiv of a variety of alkyl halides and 1 equiv of the nonionic superbase P(MeNCH2CH2)(3)N in 85-98% yields in 30 min at room temperature. The unsymmetrical active-methylene compound EtO2CCH2C(O)Me is selectively monoalkylated under the same conditions, except for the temperature, which is 0 degrees C, in 59-88% yields. The observation of selective C-rather than O-alkylation is rationalized in terms of the formation of an enolate whose negatively charged oxygen is sterically protected by a nearby HP(MeNCH2CH2)(3)N+ counterion in a tight ion pair.
• Paul; Tchelitcheff, Bulletin de la Societe Chimique de France, 1954, p. 672,674
  作者：Paul、Tchelitcheff

  DOI：——

  日期：——
• Palladium‐Catalyzed Atom‐Transfer Radical Cyclization at Remote Unactivated C(sp ³ )−H Sites: Hydrogen‐Atom Transfer of Hybrid Vinyl Palladium Radical Intermediates
  作者：Maxim Ratushnyy、Marvin Parasram、Yang Wang、Vladimir Gevorgyan

  DOI：10.1002/anie.201712775

  日期：2018.3

  A novel mild, visible‐light‐induced palladium‐catalyzed hydrogen atom translocation/atom‐transfer radical cyclization (HAT/ATRC) cascade has been developed. This protocol involves a 1,5‐HAT process of previously unknown hybrid vinyl palladium radical intermediates, thus leading to iodomethyl carbo‐ and heterocyclic structures.

  一种新型温和、可见光诱导的钯催化氢原子易位/原子转移自由基环化（HAT/ATRC）级联已经开发出来。该方案涉及先前未知的杂化乙烯基钯自由基中间体的 1,5-HAT 过程，从而产生碘甲基碳环和杂环结构。