3,3-dimethylbicyclo[4.3.0]non-1,6-en-7-one | 58567-78-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,3-dimethylbicyclo[4.3.0]non-1,6-en-7-one
• 英文别名: 5,5-dimethyl-3,4,6,7-tetrahydro-2H-inden-1-one
• CAS: 58567-78-5
• 化学式: C₁₁H₁₆O
• 分子量: 164.247
• InChiKey: IPHQPZOPPNWGQT-UHFFFAOYSA-N

物化性质

• 沸点：
  261.4±7.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3,3-dimethylbicyclo[4.3.0]non-1,6-en-7-one 在 叔丁基过氧化氢 、 bis(acetylacetonate)oxovanadium 、 dimethyl sulfide borane 、 (S)-2-甲基-CBS-恶唑硼烷 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 1.16h， 生成 (+)-(1R,6R,7R)-1,6-epoxy-3,3-dimethylbicyclo[4.3.0]nonan-7-ol
  参考文献：
  名称：

  Acid-Promoted Rearrangement of Cyclic α,β-Epoxy Acylates:  Stereoselective Synthesis of Spirocyclanes and Quaternary Carbon Centers

  摘要：

  The rearrangement reaction of alpha,beta-epoxy acylates in cyclic systems was studied. The treatment of cis-derivatives with a Lewis acid afforded rearranged products via the regioselective B-cleavage of the oxirane ring due to the electron-withdrawing nature of the acyloxy group, whereas trans-derivatives enhanced the neighboring group participation to yield only a small amount of rearranged products. This rearrangement reaction proved to be useful for the construction of st variety of spirocyclane systems or quaternary carbon centers on rings and could be applied to their syntheses as optically active forms.

  DOI：

  10.1021/jo970035q
• 作为产物：
  描述：

  6,6-Dimethyl-3-phenylsulfanyl-2,6,7,7a-tetrahydro-1H-indene 在 水 、 四氯化钛 、 溶剂黄146 作用下， 生成 3,3-dimethylbicyclo[4.3.0]non-1,6-en-7-one
  参考文献：
  名称：

  New synthetic methods. A stereocontrolled approach to cyclopentane annelation

  摘要：

  DOI：

  10.1021/ja00417a048

文献信息

• Tandem Cyclopropanation with Dibromomethane under Grignard Conditions
  作者：Gerhard Brunner、Laura Eberhard、Jürg Oetiker、Fridtjof Schröder

  DOI：10.1021/jo8007397

  日期：2008.10.3

  In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl carboxylates or vinyloxiranes. Using this methodology, numerous fragrance ingredients and their precursors were efficiently converted to the corresponding cyclopropyl carbinols.

  格氏试剂和二溴甲烷在环境温度下，在乙醚溶剂中有效地环丙酸烯丙基（和某些均烯丙基）醇镁和锂醇化物。锂（均）烯丙基醇盐在较高的Barbier条件下直接与镁和CH2Br2环丙烷化。反应速率取决于（均）烯丙基醇化物的取代方式和取决于锂的抗衡离子，其效果最佳。从α-取代的底物获得良好至优异的顺选择性，这符合交错的Houk模型。在串联反应中，环丙基甲醇是从烯丙基氧基锂或-镁中间体获得的，该中间体是通过共轭醛，酮和酯的烷基化以及烯丙基羧酸盐或乙烯基氧杂环戊烷原位生成的。使用这种方法，
• Cyclopropanation with Dibromomethane under Grignard and Barbier Conditions
  作者：Fridtjof Schröder、Gerhard Brunner、Laura Eberhard、Jürg Oetiker

  DOI：10.1055/s-0029-1216999

  日期：2009.11

  from α-substituted (homo)allyl alcohols. In tandem reactions, cyclopropyl carbinols are obtained from allyloxylithium or -magnesium intermediates, generated in situ by alkylation of conjugated aldehydes, ketones, and esters as well as from allyl esters and carbonates or vinyloxiranes. [¹] cyclopropanation - Barbier conditions - Grignard addition - alkyllithium addition - dibromomethane

  格氏试剂和二溴甲烷在环境温度下，在乙醚溶剂中有效地环丙酸烯丙基（和某些均烯丙基）镁和锂醇化物。在较高的Barbier条件下，将（均）烯丙基锂醇盐与镁和二溴甲烷直接环丙烷化。反应速率取决于（均）烯丙基醇化物的取代方式和取决于锂的抗衡离子，其效果最佳。从α-取代的（均）烯丙基醇获得良好至优异的顺选择性。在串联反应中，环丙基甲醇是从烯丙氧基锂或镁中间体获得的，该中间体是通过共轭醛，酮和酯的烷基化以及烯丙基酯和碳酸酯或乙烯基氧杂环戊烷而原位生成的。[ ¹] 环丙烷化-Barbier条件-Grignard加成-烷基锂加成-二溴甲烷
• Asymmetric synthesis of chiral spirocyclanes: Selective formation of 2-acyloxy-1-oxospiro[4.n]alkanes by regio- and stereoselective rearrangement of α,β-epoxy acylates in bicyclo[n.3.0]alkane systems
  作者：Hiromichi Fujioka、Shinji Kitagaki、Reiko Imai、Michinori Kondo、Sachi Okamoto、Yutaka Yoshida、Shuji Akai、Yasuyuki Kita

  DOI：10.1016/0040-4039(95)00517-g

  日期：1995.5

  Selective formation of 2-acyloxy-1-oxospiro[4.n]alkanes by regio- and stereoselective rearrangement of α,β-epoxy acylates in bicyclo[n.3.0]alkane systems has been achieved; the effect of the acyloxy group and stereochemistry of the starting epoxides were studied. The reaction was successfully applied to the synthesis of an optically active chiral spiro compound.

  通过在双环[n.3.0]烷烃体系中α，β-环氧酰化物的区域和立体选择性重排，实现了2-酰氧基-1-氧螺环[4.n]烷烃的选择性形成；研究了酰氧基的影响和起始环氧化物的立体化学。该反应成功地用于光学活性手性螺化合物的合成。