(1R,2S)-1-Methyl-2-vinylcyclopentanecarboxaldehyde | 81496-59-5

• 分子结构分类: 有机化合物 - 有机氧化合物 - 有机氧化物
• 英文名称: (1R,2S)-1-Methyl-2-vinylcyclopentanecarboxaldehyde
• 英文别名: (1R,2S)-2-ethenyl-1-methylcyclopentane-1-carbaldehyde
• CAS: 81496-59-5
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: LQFCLACRRXXHJC-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  (1R,2S)-1-Methyl-2-vinylcyclopentanecarboxaldehyde 在 sodium hydroxide 、 正丁基锂 、 dimethyl sulfide borane 、 4 A molecular sieve 、 水 、 双氧水 、 草酸 、 对甲苯磺酸 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 丙酮 、 乙腈 为溶剂， 反应 3.67h， 生成 (2S,3R)-3-Isopropenyl-2-[(1S,2S)-1-methyl-2-(3-methyl-but-2-enyl)-cyclopentylmethyl]-cyclopentanone
  参考文献：
  名称：

  A short enantiospecific synthesis of the ceroplastin nucleus.

  摘要：

  The tricyclic nucleus 9b of ceroplastol I and ceroplasteric acid has been synthesized stereoselectively and enantiospecifically in only 10 steps from 1-cyclopentenecarboxaldehyde. Addition of (3-methyl-3-butenyl)magnesium bromide to imine 13b and methylation with methyl iodide by Koga's procedure gave 94% of optically pure aldehyde 40 as previously described in our reiswigin A synthesis. Isomerization of the double bond of aldehyde 40 with HI afforded aldehyde 17b. Coupling of the enolate prepared from silyl enol ether 45 with aldehyde 17b gave a 1:1 mixture of 46a and 46b, which contain the complete carbon skeleton of 9b, in only three steps. Dehydration provided enones 47a and 47b. Reduction of 47a and 47b with Li/NH3 afforded saturated ketones 48at and 48bt that were reduced with LiAlH4 to the saturated alcohols 49att and 49btt. Protection of the alcohols as the TBDMS ethers and oxidative cleavage of the dienes afforded readily separable keto aldehydes 51 and 56. McMurry coupling of 51, cleavage of the silyl ether, and oxidation of the alcohol with PCC completed the synthesis of 9b.

  DOI：

  10.1021/jo00039a021
• 作为产物：
  描述：

  乙烯基溴化镁 、 (S)-2-{[1-Cyclopent-1-enyl-meth-(Z)-ylidene]-amino}-3,3-dimethyl-butyric acid tert-butyl ester 、 碘甲烷 生成 (1R,2S)-1-Methyl-2-vinylcyclopentanecarboxaldehyde
  参考文献：
  名称：

  1,2-二取代的环烷烃甲醛的不对称合成。立体选择性制备顺式和反式异构体的步骤

  摘要：

  描述了用于从非对映异构体和对映异构体纯度的相应环烯烃羧醛（）在邻位不对称合成叔碳原子和季碳原子的1,2-二取代的环烷甲醛醛（）的不对称合成方法。

  DOI：

  10.1016/s0040-4039(00)92856-9

文献信息

• Diastereoselective and enantioselective synthesis of 1,2-disubstituted cycloalkanecarboxaldehydes
  作者：Hiroshi Kogen、Kiyoshi Tomioka、Shun-Ichi Hashimoto、Kenji Koga

  DOI：10.1016/s0040-4020(01)93269-7

  日期：——

  quaternary carbon atoms in vicinal positions in their rings, is devised starting from cycloalkenecarboxal-dehydes (5) t-Leucine t-butyl ester (2, R=But), a highly effective chiral auxiliary reagent in the present method, can be recovered for recycling without any loss of optical purity Some mechanistic explanations on the stereochemical courses of the reactions are presented

  对于非对映选择性和对映选择性合成一个非常有用的方法反式-和顺-1,2-二取代cycloalkanecarboxaldehydes（反式-和顺式- 10），有用的手性合成子具有非对称叔和在其环的邻位位置上的季碳原子，被设计出发可以从本方法中的高效手性助剂-环烯烃羧醛（5）叔亮氨酸叔丁酯（2，R = Bu t）中回收而无需光学纯度损失。介绍了反应的立体化学过程
• KOGEN, HIROSHI;TOMIOKA, KIYOSHI;HASHIMOTO, SHUN-ICHI;KOGA, KENJI, TETRAHEDRON, 1981, 37, N 23, 3951-3956
  作者：KOGEN, HIROSHI、TOMIOKA, KIYOSHI、HASHIMOTO, SHUN-ICHI、KOGA, KENJI

  DOI：——

  日期：——