(4aRS,8aSR)-8a-hydroxyoctahydronaphthalen-1(2H)-one | 128893-55-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4aRS,8aSR)-8a-hydroxyoctahydronaphthalen-1(2H)-one
• 英文别名: 8a-hydroxyoctahydro-1(2H)-naphthalenone (cis isomer)；(4As,8aR)-8a-hydroxy-2,3,4,4a,5,6,7,8-octahydronaphthalen-1-one
• CAS: 128893-55-0
• 化学式: C₁₀H₁₆O₂
• 分子量: 168.236
• InChiKey: ZFOOVBJHEUWTSZ-WCBMZHEXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4aRS,8aSR)-8a-hydroxyoctahydronaphthalen-1(2H)-one 在 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三乙基硼氢化锂 、 甲基磺酰氯 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 2,3,4,5,6,7,8,8a-octahydro-1H-naphthalen-4a-ol
  参考文献：
  名称：

  Electroorganic chemistry. 140. Electroreductively promoted intra- and intermolecular couplings of ketones with nitriles.

  摘要：

  Electroreduction of gamma and delta-cyano ketones in i-PrOH with Sn cathode gave alpha-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products. Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of gamma and delta-cyano ketones in one of the key steps. Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product. The product obtained by the electroreductive intermolecular coupling of (+)-dihydrocarvone with acetonitrile has been found to be the precursor of an effective chiral ligand for the enantioselective addition of diethylzinc to aldehydes.

  DOI：

  10.1021/jo00052a036
• 作为产物：
  描述：

  4-(2-oxocyclohexyl)butanenitrile 在 Cp2TiPh 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 2.0h， 以69%的产率得到(4aRS,8aSR)-8a-hydroxyoctahydronaphthalen-1(2H)-one
  参考文献：
  名称：

  The Cp₂TiPh-Mediated Reductive Radical Cyclization of Cyanoketones and Related Reactions. Efficient Trapping of Ketyl Radicals by Cp₂TiPh-Coordinated Polar Multiple Bonds

  摘要：

  The reductive radical cyclization of cyanoketones was achieved using Cp2TiPh. The Ti(III) reagent was prepared by the sequential addition of i-PrMgCl and PhMgBr to commercial Cp2TiCl2 in this order and used effectively without isolation. The cyclization of the gamma- and delta-cyanoketones was performed in toluene at ambient temperature for several hours to give alpha-hydroxycyclopentanones and hexanones in moderate to good yields, respectively. The titanium reagent independently coordinates to both the carbonyl and cyano termini. As a result of lowering the LUMO of the cyano group upon coordination of the Ti(III) species, the irreversible cyclization successfully proceeds without formation of the unstable iminyl radical intermediate. The ester group can also be activated by the coordination of Cp2TiPh, and aromatic ketones with an ester group at the gamma position are cyclized to give the corresponding alpha-hydroxyketones.

  DOI：

  10.1021/jo982492s

文献信息

• Preparation of Cyclic .ALPHA.-Hydroxy Ketones from .DELTA.- and .EPSILON.-Keto Acids Induced by the Generation of a Novel Acyl Anion Equivalent from the Carboxyl Group.
  作者：Hatsuo MAEDA、Haruka ASHIE、Toshihide MAKI、Hidenobu OHMORI

  DOI：10.1248/cpb.45.1729

  日期：——

  An improved method for the transformation of keto acids into cyclic α-hydroxy ketones, induced by the electrochemical generation of a novel acyl anion equivalent from the carboxy group, has been developed. Both five- and six-membered rings were constructed by constant-current electrolysis of δ- and ε-keto acids in the presence of Bu3P using an undivided cell equipped with a graphite anode and a Pt cathode. Attempts to prepare four- and seven-membered ring carbocycles were unsuccessful. The electrochemical reaction was found to be highly stereoselective when cyclization took place onto cyclopentanone and substituted cyclohexanone rings. Stereochemical aspects of the formation of bicyclic products, especially those having a bicyclo[4.3.0]skeleton, are discussed.

  开发了一种改进的方法，通过电化学生成从羧基衍生出的新型酰基阴离子等价物，诱导将酮酸转化为环状α-羟基酮。通过在配有石墨阳极和铂阴极的无隔膜电池中，在Bu3P存在下对δ-和ε-酮酸进行恒流电解，构建了五元和六元环。尝试制备四元和七元环碳环未能成功。当环化反应发生在环戊酮和取代环己酮环上时，发现该电化学反应具有高度立体选择性。讨论了双环产物形成的立体化学方面，特别是具有双环[4.3.0]骨架的产物。
• Reductive Intramolecular Henry Reactions Induced by Stryker’s Reagent
  作者：Pauline Chiu、Wing Chung

  DOI：10.1055/s-2004-836044

  日期：——

  Conjugate reductions of nitroalkenes by Stryker's reagent are ensued by intramolecular aldol reactions to produce β-nitroalcohols in good yield, constituting the first examples of reductive Henry reactions.

  Stryker 试剂对硝基烯烃的共轭还原通过分子内羟醛反应进行，以良好的产率生产 β-硝基醇，构成还原性亨利反应的第一个例子。
• Polycycle construction via cascade radical fragmentation transannulation-cyclisation processes
  作者：Charles E. Mowbray、Gerald Pattenden

  DOI：10.1016/s0040-4039(00)60074-6

  日期：1993.1

  Treament of the bicyclic dienol (8) with iodosylbenzene diacetate-iodine is shown to lead to the 7,5,-tricycle (11, 81%) by way of a cascade ra

  双环二烯醇（的黄泥8）用亚碘酰苯二乙酸酯-碘被示为导致7,5，-tricycle（11通过级联RA的方式，81％）
• A Facile Construction of Bi- or Tricyclic Skeletons by Nickel-Catalyzed Stereoselective Cyclization of Alkynylcycloalkanone
  作者：Nozomi Saito、Yasuyuki Sugimura、Yoshihiro Sato

  DOI：10.1021/ol101329d

  日期：2010.8.6

  A nickel-catalyzed intramolecular cyclization of alkynylalkanone in the presence of Et(3)SiH using an NHC ligand produced various carbo- and heterocycles In a stereoselective manner. The reaction would proceed via formation of oxanickelacycle followed by sigma-bond metathesis with silane to give a bi- or tricyclic compound.
• Blackburn, Christopher; Childs, Ronald F.; Kennedy, Roger A., Canadian Journal of Chemistry, 1983, vol. 61, p. 1981 - 1986
  作者：Blackburn, Christopher、Childs, Ronald F.、Kennedy, Roger A.

  DOI：——

  日期：——