(3S,4S,7R)-4-异丙基-7-甲基-1-氧杂螺[2.5]辛烷 | 184178-86-7

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 中文名称: (3S,4S,7R)-4-异丙基-7-甲基-1-氧杂螺[2.5]辛烷
• 英文名称: (1S,4S,7R)-4-isopropyl-7-methyl-1-oxaspiro[2.5]octane
• 英文别名: (3S,4S,7R)-4-isopropyl-7-methyl-1-oxaspiro[2.5]octane；(3S,4S,7R)-7-methyl-4-propan-2-yl-1-oxaspiro[2.5]octane
• CAS: 184178-86-7
• 化学式: C₁₁H₂₀O
• 分子量: 168.279
• InChiKey: BJPUHZQRGZKFJL-OUAUKWLOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  12
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (3S,4S,7R)-4-异丙基-7-甲基-1-氧杂螺[2.5]辛烷 在 4,4'-二叔丁基苯并 、 水 、 lithium 作用下， 生成 (1S,2S,5R)-1,5-dimethyl-2-(1-methylethyl)cyclohexan-1-ol
  参考文献：
  名称：

  Chiral epoxides as a source of chiral β-oxidofunctionalised organolithium compounds: Reaction with electrophiles

  摘要：

  The reductive opening of chiral epoxides 1, 4, 7 and 11 with lithium powder and a catalytic amount of DTBB (5 mol %) in THF at -78 degrees C, followed by treatment with different electrophiles [Bu(t)CHO, PhCHO, (CH2)(5)CO, PhCOMe, CO2, H2O, D2O,] at the same temperature leads, after hydrolysis with water, to enantiomerically pure functionalised alcohols 3, 6, 9, 10 and 13. Monoprotected diols 6 and 10 give 1,2,4-triols 14 after treatment under acidic conditions in methanol, in almost quantitative yield. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0957-4166(96)00390-4
• 作为产物：
  描述：

  (-)-薄荷酮 在 碳酸氢钠 、 sodium amide 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 7.0h， 生成 (3S,4S,7R)-4-异丙基-7-甲基-1-氧杂螺[2.5]辛烷
  参考文献：
  名称：

  Synthesis and characterization of a new enantiopure hydroxylated phosphine, its rhodium(I) and (III) complexes and their performance in catalytic carbonylation

  摘要：

  The enantiomerically pure hydroxylated phosphine (1S,2S.5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol 3 was prepared in a two-step stereoselective process from the commercially available and low cost (-)-menthone. Reaction of this new ligand with the appropriate rhodium precursor gave the respective Rh(I) and Rh(III) complexes. For rhodium(I) the binuclear complex tran-P,P-bis-{mu-chlorocarbonyl[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-P]-rhodium(I)} 6 was obtained by reaction with [Rh(mu-Cl)(CO)(2)](2). For Rh(III), two isomeric edge-sharing bioctahedral (ESBO) complexes. tirans-O,O-trans-P.P-bis{(OC-6-32)-[mu-chlorodichloro[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methylcyclohexanol-O,P]rhodium(III) 7a and trans-O,O-cis-P,P-bis{(OC-6-32)-mu-chlorodichloro[(1S,2S,5R)-1-diphenyphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]rhodium(III): 7b, and the partially hydrolyzed product, trans-O,O-cis-P,P-(OC-32)- mu-chloro-mu-hydroxo-tetrachlorobis[(1S,2S,5R)-1-diphenylphosphinomethyl-2-isopropyl-5-methyl-cyclohexanol-O,P]dirhodium(III)} 8 were characterized in solid state by single-crystal X ray diffraction analysis. The O-axial-P-equatorial trans-O,O arrangements observed in compounds 7a,b and 8 are preferred over the more common O-equatorial-P-equatorial Structure, presumably due to the stereo-electronic coordination preferences of the chiral hydroxylated phosphine. To the best Of Our knowledge, the ligand arrangement observed in 7b and 8 is unique among ESBO complexes. The rhodium(I) complex 6 is active as a catalyst precursor in the hydroformylation of styrene. yielding initial turnover frequencies up to 440 h(-1) and selectivities up to 74% in the branched aldehyde. Unfortunately, no enantiomeric excesses have been observed within experimental error. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(03)00488-9

文献信息

• One-Pot Synthesis of<i>N</i>-<i>tert</i>-Butylsulfinylimines and Homoallylamine Derivatives from Epoxides
  作者：Alejandro Lahosa、Francisco Foubelo、Miguel Yus

  DOI：10.1002/ejoc.201600612

  日期：2016.8

  The reaction of epoxides with tert-butanesulfinamide in the presence of a Lewis acid, such as erbium triflate or boron trifluoride–diethyl ether, in THF as solvent, under microwave or thermal activation, produces N-tert-butylsulfinylimines in reasonable yields. Aromatic and gem-disubstituted and trisubstituted alkyl epoxides performed better than mono-alkyl-substituted compounds. After imine formation

  环氧化物与叔丁烷亚磺酰胺在路易斯酸（如三氟甲磺酸铒或三氟化硼 - 乙醚）存在下，以 THF 为溶剂，在微波或热活化下反应，以合理的产率生成 N-叔丁基亚磺酰亚胺。芳香族和双取代和三取代的烷基环氧化物比单烷基取代的化合物表现更好。亚胺形成后，随后的铟促进的烯丙基化可以在同一反应烧瓶中以单一合成操作进行，从而以通常高的产率得到高烯丙胺衍生物。
• PROCESS FOR MAKING NEO-ENRICHED p-MENTHANE COMPOUNDS
  申请人：Erman Mark B.

  公开号：US20120116113A1

  公开（公告）日：2012-05-10

  A process for making neo-enriched p-menthane intermediates is disclosed. Lewis acid-catalyzed rearrangement of an oxaspiro compound provides an aldehyde mixture comprising normal (II) and neo (III) p-menthane-3-aldehydes: with the neo aldehyde (III) as the major product. The aldehyde mixture is readily oxidized to provide the corresponding carboxylic acids, and the acids are easily converted to a host of neo-enriched p-menthane esters or amides. The esters and amides are valuable as physiological coolants.

  公开了一种制备富含新生代p-薄荷醛中间体的方法。Lewis酸催化的氧杂螺环化合物重排提供了一种包含正常(II)和新生代(III) p-薄荷醛的醛混合物：其中新生代醛(III)是主要产物。这种醛混合物容易被氧化成相应的羧酸，而这些酸则容易转化为大量的富含新生代p-薄荷酯或酰胺。这些酯和酰胺作为生理降温剂非常有价值。
• Process for making neo-enriched p-menthane compounds
  申请人：Renessenz LLC

  公开号：EP2450337A3

  公开（公告）日：2014-06-18

  A process for making neo-enriched p-menthane intermediates is disclosed. Lewis acid-catalyzed rearrangement of an oxaspiro compound provides an aldehyde mixture comprising normal (II) and neo (III) p-menthane-3-aldehydes: with the neo aldehyde (III) as the major product. The aldehyde mixture is readily oxidized to provide the corresponding carboxylic acids, and the acids are easily converted to a host of neo-enriched p-menthane esters or amides. The esters and amides are valuable as physiological coolants.

  揭示了一种制备富含新生代p-薄荷烷中间体的过程。Lewis酸催化的氧杂螺环化合物重新排列提供了包含正常（II）和新生代（III）p-薄荷烷-3-醛的醛混合物：其中新生代醛（III）为主要产物。该醛混合物容易氧化为相应的羧酸，并且这些酸易于转化为一系列富含新生代p-薄荷烷酯或酰胺。这些酯和酰胺作为生理制冷剂具有很高的价值。
• Synthesis and Structure of Chiral Silatranes Derived from Terpenes
  作者：Gabriele Wagner、Rudolf Herrmann、BjØrn Pedersen、Wolfgang Scherer

  DOI：10.1515/znb-2001-0105

  日期：2001.1.1

  Starting with the chiral pool compounds (-)-menthone, (-)-limonene, (-)-β-pinene, and (-)-carvone, new homochiral triethanolamine derivatives were obtained and converted to chi­ral silatranes. These silatranes were characterized by crystal structure analyses and NMR techniques. Conformational analyses in the solid state and in solution show that the chiral terpene residues determine the direction of the ring puckering of the silatrane moiety.

  摘要：从手性池化合物(-)-薄荷醛、(-)-柠檬烯、(-)-β-蒎烯和(-)-香茜醛出发，得到了新的同手性三乙醇胺衍生物，并转化为手性硅氮环烷化合物。通过晶体结构分析和NMR技术对这些硅氮环烷进行了表征。固态和溶液中的构象分析表明，手性萜烯残基决定了硅氮环烷部分的环褶曲方向。
• INTERCONVERSION BETWEEN ISOMERIC P-MENTHANE-3-CARBOXYLIC ACIDS
  申请人：Erman Mark B.

  公开号：US20120283469A1

  公开（公告）日：2012-11-08

  A process for interconversion between WS-1 and neo-WS-1 by heating to a temperature in a range of from 60 degrees Celsius to 250 degrees Celsius. The heating can be done in the presence of an acid catalyst. Starting from practically pure (=98%) WS-1, or mixtures of WS-1 and neo-WS-1, practically pure (=98%) neo-WS-1 can be obtained. Starting from practically pure (=98%) neo-WS-1, or mixtures of WS-1 and neo-WS-1, practically pure (=98%) WS-1 can be obtained.

  通过加热至60摄氏度至250摄氏度的温度范围进行WS-1和neo-WS-1之间的互变过程。加热可以在酸性催化剂存在的情况下进行。从实际纯度（≥98%）的WS-1开始，或者从WS-1和neo-WS-1的混合物开始，可以获得实际纯度（≥98%）的neo-WS-1。从实际纯度（≥98%）的neo-WS-1开始，或者从WS-1和neo-WS-1的混合物开始，可以获得实际纯度（≥98%）的WS-1。