4-(2-oxocyclohexyl)pentanal | 200728-35-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-(2-oxocyclohexyl)pentanal
• 英文别名: 5-(2-Oxocyclohexyl)pentanal
• CAS: 200728-35-4
• 化学式: C₁₁H₁₈O₂
• 分子量: 182.263
• InChiKey: FFWDSFCRNGXWSK-UHFFFAOYSA-N

物化性质

• 沸点：
  297.0±13.0 °C(Predicted)
• 密度：
  0.972±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-ethoxy-1-(tert-butyldimethylsilyloxy)ethene 、 4-(2-oxocyclohexyl)pentanal 在 二溴双(2,3,4,5,6-五氟苯基)锡烷 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以64%的产率得到Ethyl 2-[1-[tert-butyl(dimethyl)silyl]oxy-2-(5-oxopentyl)cyclohexyl]acetate
  参考文献：
  名称：

  Unusual Preference for Ketone and Reversal of Chemoselectivity in Lewis Acid-Catalyzed Aldol Reaction of Ketene Silyl Acetal

  摘要：

  Ketene silyl acetals undergo facile reaction with ketones in the presence of a Lewis acid such as (C6F5)(2)SnBr2, TMSOTf, or Sc(OTf)(3). This unique reactivity allows ketones to react in preference to aldehydes or acetals in competitive aldol-type reactions. Upon treatment with keto aldehydes or keto acetals, ketene silyl acetals provide single products derived from the exclusive reaction with the ketonic function. Particularly noteworthy is the discrimination of ketones from aldehydes in naked forms. It has been proved that such bias results from the differentiated recognition of ketone and aldehyde carbonyls. The ternary system consisting of ketene silyl acetal, carbonyl, and an appropriate Lewis acid is crucial for achieving the effective differentiation.

  DOI：

  10.1021/jo981218v
• 作为产物：
  描述：

  (+/-)-5-(2-oxocyclohexyl)pentanoic acid 在 甲烷磺酸 、 三丁基膦 、 苄基三乙基氯化铵 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到4-(2-oxocyclohexyl)pentanal
  参考文献：
  名称：

  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.

  摘要：

  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。

  DOI：

  10.1248/cpb.45.1729

文献信息

• Parallel recognition by virtue of differentiation between ketone and aldehyde
  作者：Jian-xie Chen、Junzo Otera

  DOI：10.1016/s0040-4039(98)00039-2

  日期：1998.3

  The concept of parallel recognition has been applied to differentiate between ketone and aldehyde: (C6F5)2SnBr2-catalyzed Mukaiyama-aldol reaction of a mixture of these two carbonyl substrates with a mixture of enol silyl ethers derived from esters and ketones results in exclusive formation of ketone/ester and aldehyde/ketone aldol adducts, respectively.

  平行识别的概念已用于区分酮和醛：（C 6 F 5）2 SnBr 2催化的这两种羰基底物的混合物与衍生自酯和酮的烯醇甲硅烷基醚的混合物的Mukaiyama- aldol反应分别导致酮/酯和醛/酮羟醛加合物的排他性形成。
• Parallel recognition by virtue of differentiation between carbonyls, acetals and enones
  作者：Jian-xie Chen、Katsumasa Sakamoto、Akihiro Orita、Junzo Otera

  DOI：10.1016/s0040-4020(98)00462-1

  日期：1998.7

  are performed simultaneously on separate reaction sites, has been advanced. Ketones/α,β-enones and aldehydes/acetals are able to react selectively with different silyl nucleophiles in parallel. The subtle differentiation between the substrates possessing similar reactivities has recourse to the strong preference of ketene silyl acetal for ketones/α,β-enones.

  提出了“并行识别”，一种用于压缩合成过程的新概念，其中在不同的反应位点同时进行不同的转化。酮/α，β-烯酮和醛/缩醛能够选择性地与不同的甲硅烷基亲核试剂平行反应。具有相似反应性的底物之间的细微差别归因于乙烯酮甲硅烷基乙缩醛对酮/α，β-烯酮的强烈偏爱。
• DANGELO, JEAN;FERROUD, CLOTILDE;RICHE, CLAUDE;CHIARONI, ANGELE, TETRAHEDRON. LETT., 30,(1989) N7, C. 6511-6514
  作者：DANGELO, JEAN、FERROUD, CLOTILDE、RICHE, CLAUDE、CHIARONI, ANGELE

  DOI：——

  日期：——
• 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。
• Unusual Preference for Ketone and Reversal of Chemoselectivity in Lewis Acid-Catalyzed Aldol Reaction of Ketene Silyl Acetal
  作者：Jian-xie Chen、Katsumasa Sakamoto、Akihiro Orita、Junzo Otera

  DOI：10.1021/jo981218v

  日期：1998.12.1

  Ketene silyl acetals undergo facile reaction with ketones in the presence of a Lewis acid such as (C6F5)(2)SnBr2, TMSOTf, or Sc(OTf)(3). This unique reactivity allows ketones to react in preference to aldehydes or acetals in competitive aldol-type reactions. Upon treatment with keto aldehydes or keto acetals, ketene silyl acetals provide single products derived from the exclusive reaction with the ketonic function. Particularly noteworthy is the discrimination of ketones from aldehydes in naked forms. It has been proved that such bias results from the differentiated recognition of ketone and aldehyde carbonyls. The ternary system consisting of ketene silyl acetal, carbonyl, and an appropriate Lewis acid is crucial for achieving the effective differentiation.