(3aSR,7aRS)-3a-hydroxyhexahydro-1H-inden-4(2H)-one | 144126-68-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aSR,7aRS)-3a-hydroxyhexahydro-1H-inden-4(2H)-one
• 英文别名: (3aR,7aS)-3a-hydroxy-2,3,5,6,7,7a-hexahydro-1H-inden-4-one
• CAS: 144126-68-1
• 化学式: C₉H₁₄O₂
• 分子量: 154.209
• InChiKey: SULBTBHVGSMRQA-VXNVDRBHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 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：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (3aSR,7aRS)-3a-hydroxyhexahydro-1H-inden-4(2H)-one 在 lithium aluminium tetrahydride 、 甲基磺酰氯 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 9.0h， 生成 (1α,6α)-Bicyclo<4.3.0>nonan-1-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：

  3-cyanopropylcyclopentanone 在 Cp2TiPh 、 水 作用下， 生成 (3aSR,7aRS)-3a-hydroxyhexahydro-1H-inden-4(2H)-one
  参考文献：
  名称：

  Cp2TiPh-coordinated cyano and ester groups as efficient ketyl radical acceptors in the reductive radical cyclization of γ- and δ-cyano ketones and δ-keto esters

  摘要：

  Cp2TiPh促进了γ-和δ-氰基酮及δ-酮酯的还原自由基环化，得到α-羟基环状酮，产率适中到良好；钛试剂与酮和氰基或酯末端均形成配位，氰基或酯基团的LUMO因此降低，环化过程不可逆进行，不会形成不稳定的亚胺或烷氧自由基中间体。

  DOI：

  10.1039/a800661j

文献信息

• Cp2TiPh-coordinated cyano and ester groups as efficient ketyl radical acceptors in the reductive radical cyclization of γ- and δ-cyano ketones and δ-keto esters
  作者：Yoshihiko Yamamoto、Daisuke Matsumi

  DOI：10.1039/a800661j

  日期：——

  Cp2TiPh promotes the reductive radical cyclization of γ- and δ-cyano ketones and δ-keto esters to give α-hydroxycycloalkanones in moderate to good yields; the titanium reagent coordinates to both the ketone and the cyano or ester terminus, the LUMO of the cyano or ester group is thus lowered, and cyclization proceeds irreversibly without formation of the unstable iminyl or alkoxy radical intermediates.

  Cp2TiPh促进了γ-和δ-氰基酮及δ-酮酯的还原自由基环化，得到α-羟基环状酮，产率适中到良好；钛试剂与酮和氰基或酯末端均形成配位，氰基或酯基团的LUMO因此降低，环化过程不可逆进行，不会形成不稳定的亚胺或烷氧自由基中间体。
• Intramolecular Ketone−Nitrile Reductive Coupling Reactions Promoted by Samarium(II) Iodide
  作者：Gary A. Molander、Chad N. Wolfe

  DOI：10.1021/jo981537m

  日期：1998.11.1

  Samarium(II) iodide (SmI2) has been successfully utilized as a reducing agent for the intramolecular coupling of ketones with nitriles. The use of visible light to promote the reductive coupling represents an improvement over previously reported protocols. The procedure also avoids overreduction of the resulting alpha-hydroxy ketones. Monocyclic, fused bicyclic, and bridged bicyclic alpha-hydroxy ketones composed of a number of substitution patterns have been synthesized in moderate to excellent yield via this method. A sequential reaction consisting of a nucleophilic acyl substitution followed by a ketyl-nitrile coupling has also been accomplished.
• 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.
• SHONO, TATSUYA;KISE, NAOKI, TETRAHEDRON LETT., 31,(1990) N, C. 1303-1306
  作者：SHONO, TATSUYA、KISE, NAOKI

  DOI：——

  日期：——
• Electroorganic chemistry. 140. Electroreductively promoted intra- and intermolecular couplings of ketones with nitriles.
  作者：Tatsuya Shono、Naoki Kise、Taku Fujimoto、Naoto Tominaga、Hiroshi Morita

  DOI：10.1021/jo00052a036

  日期：1992.12

  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.