1-氧杂螺[4.5]癸烷-6-酮 | 129529-81-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 中文名称: 1-氧杂螺[4.5]癸烷-6-酮
• 英文名称: (S*)-1-oxaspiro<4.5>decan-6-one
• 英文别名: 1-oxaspiro<4.5>decan-6-one；1-oxaspiro[4.5]decan-6-one
• CAS: 129529-81-3
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: YOJIYPFKKGAVKW-UHFFFAOYSA-N

物化性质

• 沸点：
  267.4±23.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-氧杂螺[4.5]癸烷-6-酮 在 4-二甲氨基吡啶 、 indium 、 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 二甲基硫 、 双氧水 、 臭氧 、 三乙胺 、 对甲苯磺酰氯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 170.0h， 生成 (5S,6S)-1,7-Dioxadispiro[4.0.4.4]tetradecan-11-one
  参考文献：
  名称：

  Definition of Several Control Elements Relevant to the Stereodefined Serial Elaboration of Belted Poly(spirotetrahydrofurans) Fitted with a Cyclohexane Core

  摘要：

  The stereochemistry of the condensations of 2-cyclohexenones, alpha-arylidenecyclohexanones, and alpha-(tert-butyldimethylsiloxy)cyclohexanones carrying one or two (both syn and anti) spirotetra-hydrofuran units adjacent to the carbonyl with allyl organometallics (especially indium) and with the Normant reagent (ClMgO(CH2)(3)MgCl) is described. Good levels of anti stereoselection are observed in the alpha-arylidene series. Subsequent cyclization generates a second (or third) tetrahydrofuran ring possessing trans vicinal oxygens. Useful levels of matched and mismatched diastereoselection are also attainable by prior alpha-oxygenation, The intrinsic differences in diastereomer production between indium and magnesium organometallics are highlighted. A clear distinction regarding the anticipated direction of stereoselectivity is made on the grounds of chelation capabilities and the intra- or intermolecularity of carbon-carbon bond formation. Finally, the two protocols that are described in detail are shown to be iterative, a feature that augurs well for ultimately accessing the eight possible hexaspirocyclohexanes in an efficient and stereocontrolled manner.

  DOI：

  10.1021/jo960962h
• 作为产物：
  描述：

  1-(4,5-dihydrofuran-2-yl)cyclopentanol 在 Dowex-50X 作用下， 以 二氯甲烷 为溶剂， 以71%的产率得到1-氧杂螺[4.5]癸烷-6-酮
  参考文献：
  名称：

  Paquette, Leo A.; Lawhorn, David E.; Teleha, Christopher A., Heterocycles, 1990, vol. 30, # 2, p. 765 - 769

  摘要：

  DOI：

文献信息

• Oxacycle Synthesis via Intramolecular Reaction of Carbanions and Peroxides
  作者：Rachel Willand-Charnley、Benjamin W. Puffer、Patrick H. Dussault

  DOI：10.1021/ja5026276

  日期：2014.4.23

  The intramolecular reaction of dialkyl peroxides with carbanions, generated via chemoselective metal-heteroatom exchange or deprotonation, provides a new approach to cyclic ethers. Applied in tandem with C–C bond formation, the strategy enables a one-step annelation to form oxaospirocycles.

  通过化学选择性金属-杂原子交换或去质子化产生的二烷基过氧化物与碳负离子的分子内反应提供了一种新的环醚方法。该策略与 C-C 键的形成一起应用，可以一步退火形成氧杂螺环。
• π-Facial Diastereoselection in the 1,2-Addition of Allylmetal Reagents to 2-Methoxycyclohexanone and Tetrahydrofuranspiro-(2-cyclohexanone)
  作者：Leo A. Paquette、Paul C. Lobben

  DOI：10.1021/ja9536835

  日期：1996.1.1

  stereochemical course of the 1,2-addition of several allylmetal reagents and of the Normant Grignard [ClMgO(CH2)3MgCl] to 2-methoxycyclohexanone and tetrahydrofuranspiro-(2-cyclohexanone) has been determined. In four of the six substrates examined, a 4-tert-butyl group is present to serve as a conformational anchor. The neighboring methoxyl substituent is shown to be capable of engaging effectively in

  已经确定了几种烯丙基金属试剂和 Normant Grignard [ClMgO(CH2)3MgCl] 的 1,2-加成到 2-甲氧基环己酮和四氢呋喃螺-(2-环己酮) 的立体化学过程。在检测的六种底物中的四种中，存在一个 4-叔丁基作为构象锚。相邻的甲氧基取代基显示出能够有效参与螯合，尽管特殊情况可能另有规定。涉及烯丙基试剂作为水溶液中的亲核试剂的实验表明，水的存在不会抑制螯合控制的操作，这通常大大超过在无水介质中使用相应的镁、铈和铬试剂所能达到的效果。
• Spiroketals via oxidative rearrangement of enol ethers
  作者：David L. Waller、Corey R. J. Stephenson、Peter Wipf

  DOI：10.1039/b612992g

  日期：——

  Oxidative rearrangement of cyclic enol ethers leads to alpha-alkoxyesters. In the presence of a neighboring spiroether, this approach provides a stereoselective access to spiroketals. A modified proposal for the biosynthesis of acutumine is presented.

  环状烯醇醚的氧化重排产生α-烷氧基酯。在存在相邻的螺醚的情况下，该方法提供了对螺环酮的立体选择通道。提出了修改后的方案，用于合成金盏花。
• Radical cyclizations of diosphenol ω-haloalkyl ethers to oxabicycloalkanones
  作者：Anthony A. Ponaras、Ömer Zaim

  DOI：10.1016/s0040-4039(00)60470-7

  日期：1993.4

  Radical cyclization of diosphenol omega-haloalkyl ethers gives spiro- and fused oxabicycloalkanones.
• Alkoxy radical accelerated β-fragmentation of alcohols and lactols
  作者：James H Rigby、Anne Payen、Namal Warshakoon

  DOI：10.1016/s0040-4039(01)00121-6

  日期：2001.3

  Treatment of alcohols and lactols with Pb(OAc)(4)/Cu(OAc)(2) in refluxing benzene provides the corresponding delta -unsaturated carbonyl products. (C) 2001 Elsevier Science Ltd. All rights reserved.