trans-5-methyl-3-butylcyclohexanone

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: trans-5-methyl-3-butylcyclohexanone
• 英文别名: (S,S)-3-n-butyl-5-methylcyclohexanone；(3S,5S)-3-butyl-5-methylcyclohexan-1-one
• 化学式: C₁₁H₂₀O
• 分子量: 168.279
• InChiKey: LHRQCMMUTUBJTL-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  正丁基锂 、 5-甲基环己-2-烯-1-酮 在 1.) CuCN 作用下， 生成 trans-5-methyl-3-butylcyclohexanone
  参考文献：
  名称：

  Unexpectedcis-Selective 1,4-Addition Reaction of Lower Order Cyanocuprates to Optically Active 5-(tert-Butyldimethylsiloxy)-2-cyclohexenone

  摘要：

  A remarkable cis selectivity has been observed in the 1,4-addition of lower order primary and secondary alkylcyanocuprates to 5-silyloxy- and 5-benzyloxy-substituted cyclohexenones. This enables the preparation of both enantiomers of the corresponding 5-alkyl-substituted cyclohexenones (S)- and (R)-3 by the reaction of the readily available 5-(tert-butyldimethylsiloxy)-2-cyclohexenone (1) with either the lower or higher order cyanocuprate. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene.

  DOI：

  10.1002/(sici)1521-3773(19980817)37:15<2099::aid-anie2099>3.0.co;2-u

文献信息

• Isotope Effects and the Mechanism of Chlorotrimethylsilane-Mediated Addition of Cuprates to Enones
  作者：Doug E. Frantz、Daniel A. Singleton

  DOI：10.1021/ja993373c

  日期：2000.4.1

  Kinetic isotope effects were determined for the chlorotrimethylsilane-mediated reactions of cyclohexenone with lithium dibutylcuprate in tetrahydrofuran and with lithium butyl(tert-butylethynyl)cuprate in ether. For the reaction in tetrahydrofuran, the observation of a significant carbonyl oxygen isotope effect (16k/17k = 1.018−1.019) and small olefinic carbon isotope effects (12k/13k = 1.003−1.008)

  测定了三甲基氯硅烷介导的环己烯酮与二丁基铜酸锂在四氢呋喃中和与丁基（叔丁基乙炔基）铜酸锂在乙醚中的反应的动力学同位素效应。对于四氢呋喃中的反应，观察到显着的羰基氧同位素效应 (16k/17k = 1.018−1.019) 和小的烯烃碳同位素效应 (12k/13k = 1.003−1.008) 与中间体 π 的限速硅烷化反应一致-复杂的。模型反应的理论预测同位素效应支持这一结论。氯三甲基硅烷与氯二甲基苯基硅烷的相对反应性研究也支持限速硅烷化。对产物形成不存在显着的丁基碳同位素影响表明铜酸丁基在导致产物测定步骤的中间体中是不等价的。在乙醚中，同位素效应恢复到与先前在环己烯酮与...
• Chiral copper amine complexes
  申请人：Brigham Young University

  公开号：US05134238A1

  公开（公告）日：1992-07-28

  Disclosed herein is a class of chiral copper-amine complexes of the formula R(L*) CuLi in which L* is selected from: ##STR1## In this formula, R is a transferable ligand, which can be alkyl, aryl or aralkyl. M is a metal ion such as Li, Na, K, Cs, Rb, Be, Mg and other metal ions from the first two columns of the periodic table. R.sub.1 is straight chain alkyl, R.sub.2 is aryl or substituted aryl and R.sub.3 and R.sub.4 form a heterocyclic ring or a substituted heterocyclic ring with 4 to 8 members including oxygen and sulfur. Such complexes react with .alpha.,.beta.-unsaturated ketones, aldehydes, esters and other carbonyl containing compounds such that R is transferred to the 3 position enantioselectively as shown below. ##STR2## Such complexes react with .alpha.,.beta.-unsaturated ketones in the presence of trialkysilyl halides to give silyl enol ether in which R is substituted in the 3 position as shown below. ##STR3##

  本文揭示了一类手性铜胺络合物，化学式为R（L*）CuLi，其中L*选自：##STR1## 在此公式中，R是可转移的配体，可以是烷基，芳基或芳基烷基。M是金属离子，如Li，Na，K，Cs，Rb，Be，Mg和周期表前两列中的其他金属离子。R.sub.1是直链烷基，R.sub.2是芳基或取代芳基，R.sub.3和R.sub.4形成一个含氧和硫的4至8个成员的杂环或取代杂环。这种络合物与α，β-不饱和酮，醛，酯和其他含羰基的化合物反应，使R在选择性地转移到3位置，如下所示。##STR2## 这种络合物与α，β-不饱和酮在三烷基硅基卤化物存在下反应，生成硅烷基烯醇醚，其中R在3位置被取代，如下所示。##STR3##
• Russell, Glen A.; Baik, Woonphil; Ngoviwatchai, Preecha, Acta Chemica Scandinavica, 1990, vol. 44, # 2, p. 170 - 177
  作者：Russell, Glen A.、Baik, Woonphil、Ngoviwatchai, Preecha、Kim, Byeong Hyo

  DOI：——

  日期：——
• US5134238A
  申请人：——

  公开号：US5134238A

  公开（公告）日：1992-07-28
• Unexpectedcis-Selective 1,4-Addition Reaction of Lower Order Cyanocuprates to Optically Active 5-(tert-Butyldimethylsiloxy)-2-cyclohexenone
  作者：Georges Hareau-Vittini、Shinichi Hikichi、Fumie Sato

  DOI：10.1002/(sici)1521-3773(19980817)37:15<2099::aid-anie2099>3.0.co;2-u

  日期：1998.8.17

  A remarkable cis selectivity has been observed in the 1,4-addition of lower order primary and secondary alkylcyanocuprates to 5-silyloxy- and 5-benzyloxy-substituted cyclohexenones. This enables the preparation of both enantiomers of the corresponding 5-alkyl-substituted cyclohexenones (S)- and (R)-3 by the reaction of the readily available 5-(tert-butyldimethylsiloxy)-2-cyclohexenone (1) with either the lower or higher order cyanocuprate. DBU=1,8-diazabicyclo[5.4.0]undec-7-ene.