(5S,6S)-1,7-Dioxadispiro[4.0.4.4]tetradecan-11-one | 141412-01-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢呋喃
• 英文名称: (5S,6S)-1,7-Dioxadispiro[4.0.4.4]tetradecan-11-one
• 英文别名: (5S,6S)-4,7-dioxadispiro[4.0.46.45]tetradecan-11-one
• CAS: 141412-01-3
• 化学式: C₁₂H₁₈O₃
• 分子量: 210.273
• InChiKey: UWMNSJMFQALIFU-NWDGAFQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (5S,6S)-1,7-Dioxadispiro[4.0.4.4]tetradecan-11-one 在 对甲苯磺酸 作用下， 以 氯仿 为溶剂， 反应 21.0h， 生成 (5R,6S)-1,7-Dioxa-dispiro[4.0.4.4]tetradecan-11-one
  参考文献：
  名称：

  Analysis of the Conformational Nature, Resolvability, and Thermal Racemization of Hetero 2,3-Dispiro Cyclohexanones. The Weighting of Carbonyl/C-X Stabilization Relative to the Electronic Interaction between the Vicinal Electronegative Substituents

  摘要：

  A series of hetero 2,3-dispiro cyclohexanones has been prepared. The conformations of the syn and anti isomers were assessed in the solid state, in solution, and in the gas phase (the latter by molecular mechanics calculations). The results are discussed in the light of steric, dipole, and gauche interactions; steric contributions give evidence of controlling DELTAG(eq). On a different front, the syn/anti pairs were found to interconvert when heated in the presence of a catalytic amount of acid. Three representative examples of these chiral molecules were resolved and complete racemization was observed to result under the conditions of equilibration. A push-pull fragmentation of the cyclohexanone ring is proposed to account for these observations, with the tethered oniom ion-enol pair reclosing to reconstitute the original, although stereochemically scrambled, structure. The intervention of the thionium ion intermediates is less thermodynamically favorable than that of oxonium ions, as expected.

  DOI：

  10.1021/ja00081a010
• 作为产物：
  描述：

  (5R,6S)-1,7-Dioxa-dispiro[4.0.4.4]tetradecan-11-one 在 对甲苯磺酸 作用下， 以 氯仿 为溶剂， 反应 48.0h， 生成 (5S,6S)-1,7-Dioxadispiro[4.0.4.4]tetradecan-11-one
  参考文献：
  名称：

  Regio- and stereochemical course of the ring expansion of bridged bicyclic ketones to spirocyclic .alpha.-keto tetrahydrofurans.

  摘要：

  The regio- and stereochemical aspects of oxonium-promoted pinacol-like rearrangements have been investigated starting from the bridged bicyclic ketones (+/-)-norcamphor, (1R)-(-)-fenchone, and (1R)-(-)-3,3-dimethyl-1-vinyl-2-norbornanone. 1,2-Addition of 5-lithio-2,3-dihydrofuran to these substrates provided alcohols that smoothly underwent acid-catalyzed ring expansion. Whereas bridgehead carbon migration was observed in the first and third examples, the alternative available 1,2 Wagner-Meerwein shift operated in the fenchone series. In every instance, a substantial kinetic preference for formation of the O-exo spirotetrahydrofuranyl ketone was noted. Positioning of the dihydrofuranyl unit in sterically congested endo environments as accomplished by condensation of the alpha-lithio vinyl ether with (1R)-(+)-camphor, (1S)-(+)-7,7-dimethyl-1-vinyl-2-norbornanone, and (1s)-(-)-apocamphor was accompanied by increased hydrolytic sensitivity. Second-stage ring expansion of two of the spirocyclic ketones was characterized by continued adherence to anticipated migratory aptitudes. However, loss of stereochemistry occurred both at the original alpha-carbon and at the newly introduced stereogenic center. These observations and relevant control experiments are most consistent with a push-pull fragmentation scheme leading to a ring-opened oxonium ion-enol pair that, because they are tethered, find it possible to cyclize. Prior to final bonding, either terminus may rotate relative to the other. The kinetic and thermodynamic interrelationships of these phenomena are discussed.

  DOI：

  10.1021/jo00040a042

文献信息

• <i>trans,anti,trans</i>-Tetra(spirotetrahydrofuranyl)cyclohexane-1,2-dione. Stereocontrolled Synthesis and Definition of Its Susceptibility to Photoisomerization
  作者：Leo A. Paquette、Timothy B. Lowinger、David G. Bolin、Bruce M. Branan

  DOI：10.1021/jo960961p

  日期：1996.1.1

  2-addition to an alpha-oxy substituted cyclohexanone. The successful pathway is dependent on the ability of osmium tetraoxide to add (slowly) across the double bond of the cyclohexene precursor. The highly substituted 1,2-cyclohexanedione is quite sensitive to light and rearranges by means of an interesting photoisomerization process to a laterally fused pyran system. A likely mechanistic pathway for this intramolecular

  标题α-二酮（18）已以立体控制方式合成。以扩展的反式方式引入四个连续的螺环醚氧的能力取决于Normant试剂（ClMgCH（2）CH（2）CH（2）OMgCl）在将1,2-加成至α-氧基取代的环己酮。成功的途径取决于四氧化跨环己烯前体双键（缓慢）添加的能力。高度取代的1,2-环己二酮对光非常敏感，并通过有趣的光异构化过程重排为侧向融合的吡喃体系。提出了这种分子内异构化的可能的机理途径。
• Definition of Several Control Elements Relevant to the Stereodefined Serial Elaboration of Belted Poly(spirotetrahydrofurans) Fitted with a Cyclohexane Core
  作者：Leo A. Paquette、Marshall Stepanian、Uppuluri V. Mallavadhani、Timothy D. Cutarelli、Timothy B. Lowinger、Horst Jan Klemeyer

  DOI：10.1021/jo960962h

  日期：1996.1.1

  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.
• Heteroatomic Effects on the Acid-Catalyzed Rearrangements of Dispiro[4.0.4.4]tetradeca-11,13-dienes
  作者：Bruce M. Branan、Leo A. Paquette

  DOI：10.1021/ja00096a024

  日期：1994.8

  The synthesis of dispiro [4.0.4.4]tetradeca-11,13-dienes containing one or two heteroatoms (O,S) is described. In all cases, a suitably functionalized cyclohexanone served as the precursor. Bromination-dehydrobromination delivered the cyclohexenone, which was subjected to 1,2-reduction and elimination by reaction with 2,4-dinitrobenzenesulfenyl chloride and thermal activation. The pathways by which the 1,3-cyclohexadienes undergo acid-catalyzed isomerization have been identified. The choice between aromatization and conversion to a [4.4.4]propelladiene gives evidence for being dependent on an interplay between steric and electronic factors. The generation of a transient oxonium ion causes both pathways to operate at approximately equivalent levels. When a thermodynamically less favorable thionium ion intermediate is involved, selectivity increases to the point where only aromatization occurs in the presence of p-toluenesulfonic acid. A neighboring sulfhydryl group is shown to be capable of intercepting the spirocyclic carbocationic intermediate. The regiochemistry of the epoxidation of 30 and the stereoselectivity of Diels-Alder cycloaddition of the [4.4.4]propelladienes to N-methyltriazolinedione are also detailed.
• Synthesis and molecular structure of belted spirocyclic tetrahydrofurans, a new class of preorganized hosts for cations
  作者：Leo A. Paquette、Joanna T. Negri、Robin D. Rogers

  DOI：10.1021/jo00040a041

  日期：1992.7

  The preparation and binding properties of spirocyclic tetrahydrofurans 7-11 are described. The condensation of cyclopentanone with 5-lithio-2,3-dihydrofuran (12) provided an alcohol which readily rearranged to ketone 14 under acidic conditions. ''Capping'' of the carbonyl group in 14 so as to generate a second spiro tetrahydrofuran subunit gave rise to 7 and 8. Starting with cyclobutanone, 2-fold ring expansion involving 12 provided the key reactions leading to 22 and 23, which were 'capped' as before. Crystal structure data are available for 9, 11, and 22. In addition, the variable-temperature NMR behavior of 7 and 10 was quantified by means of 2-D measurements. A detailed analysis is presented that shows the gauche effect to be of major importance in dictating the major conformation adopted by these ionophores. The binding properties of 7-11 have been assayed. Considerable variation was found, the efficiency being critically dependent upon the number of oxygen atoms, the relative stereochemistry of the C-O bonds, and the relative ease of conformational readjustment necessary to achieve proper organization around the oxophilic metal ion.
• NEGRI, JOANNA T.;ROGERS, ROBIN D.;PAQUETTE, LEO A., J. AMER. CHEM. SOC., 113,(1991) N3, C. 5073-5075
  作者：NEGRI, JOANNA T.、ROGERS, ROBIN D.、PAQUETTE, LEO A.

  DOI：——

  日期：——