N-(2-carbomethoxy-1-cyclohexen-1-yl)-(S)-valine tert-butyl ester | 89656-79-1

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: N-(2-carbomethoxy-1-cyclohexen-1-yl)-(S)-valine tert-butyl ester
• 英文别名: methyl 2-[[(2S)-3-methyl-1-[(2-methylpropan-2-yl)oxy]-1-oxobutan-2-yl]amino]cyclohexene-1-carboxylate
• CAS: 89656-79-1
• 化学式: C₁₇H₂₉NO₄
• 分子量: 311.422
• InChiKey: NFARLHNDQOYNDU-AWEZNQCLSA-N

物化性质

• 沸点：
  402.1±45.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.76
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-(2-carbomethoxy-1-cyclohexen-1-yl)-(S)-valine tert-butyl ester 在 platinum(IV) oxide 吡啶 、 氢氧化钾 、 氯化亚砜 、 氢气 、 碘 、 锌 作用下， 以 乙醚 、 苯 为溶剂， 反应 22.0h， 生成 ((1R)-2c-carboxy-2t-methyl-cyclohex-r-yl)-acetic acid
  参考文献：
  名称：

  Stereoselective reactions. XXI. Asymmetric alkylation of α-alkyl β-keto esters to α,α-dialkyl β-keto esters having either (R)- or (S)-chiral quaternary center depending on the solvent system

  摘要：

  Asymmetric alkylation reaction of chiral enamines prepared from alpha-alkyl beta-keto esters and (S)-valine tert-butyl ester leading to either enantiomer is described. Lithiated chiral enamines can be alkylated with alkyl halides in a toluene solvent in the presence of HMPA to give, after hydrolysis, alpha,alpha-dialkyl beta-keto esters in 70-99%ee. The reactions in the presence of THF, dioxolane, or trimethylamine. instead of HMPA, afford the corresponding antipodes with enantiomeric purities of 44-92%ee. The present method provides a procedure for the synthesis of both enantiomers of alpha,alpha-dialkyl beta-keto esters in high enantiomeric purities starting from the same chiral enamines.

  DOI：

  10.1016/s0040-4020(01)80346-x
• 作为产物：
  描述：

  L-缬氨酸叔丁酯盐酸盐 、 2-氧环己烷羧酸甲酯 生成 N-(2-carbomethoxy-1-cyclohexen-1-yl)-(S)-valine tert-butyl ester
  参考文献：
  名称：

  α-烷基β-酮酯的不对称烷基化

  摘要：

  非对映选择性烷基化脱硫烯胺减少部分 d'α-烷基 β-cetoesters et du (S)-valinate de t-butyle

  DOI：

  10.1021/ja00321a050

文献信息

• Asymmetric oxidation of β-ketoesters with benzoyl peroxide; enantioselective formation of protected tertiary alcohols
  作者：Junning Lee、Shunichi Oya、John K. Snyder

  DOI：10.1016/s0040-4039(00)79421-4

  日期：1991.10

  Asymmetric oxidation of β-ketoesters by the benzoyl peroxide quench of their lithioenamines formed with (S)-valine-t-butyl esters has been accomplished with good enantioselectivity for the formation of tertiary benzoate esters. This procedure thus enables generation of tertiary alcohols in protected form.

  通过过氧化苯甲酰猝灭由（S）-缬氨酸-叔丁酯形成的它们的硫代烯胺，β-酮酸酯的不对称氧化对于形成叔苯甲酸酯具有良好的对映选择性。因此，该方法使得能够生成保护形式的叔醇。
• Construction of contiguous quaternary and tertiary carbon centres via the asymmetric Michael reaction
  作者：Kiyoshi Tomioka、K?suke Yasuda、Kenji Koga

  DOI：10.1039/c39870001345

  日期：——

  Michael reactions of chiral lithioenamines of α-alkyl β-oxo esters with methyl ethylidenemalonate afforded, after hydrolysis, adducts having contiguous quaternary and tertiary carbon centres, with nearly complete enantio- and diastereo-selectivity.

  水解后，α-烷基β-氧代酯的手性硫代烯胺与亚乙基甲基丙二酸酯的迈克尔反应提供了具有连续的季碳和叔碳中心，几乎完全对映和非对映选择性的加合物。
• Asymmetric alkylation of .alpha.-alkyl .beta.-keto esters
  作者：Kiyoshi Tomioka、Kaori Ando、Yutaka Takemasa、Kenji Koga

  DOI：10.1021/ja00321a050

  日期：1984.5

  Diastereoselective alkylation de lithio enamines obtenues a partir d'α-alkyl β-cetoesters et du (S)-valinate de t-butyle

  非对映选择性烷基化脱硫烯胺减少部分 d'α-烷基 β-cetoesters et du (S)-valinate de t-butyle
• Factors controlling the diastereoface selectivity in the complementary asymmetric alkylation of α-alkyl β-keto esters
  作者：Kiyoshi Tomioka、Kaori Ando、Yutaka Takemasa、Kenji Koga

  DOI：10.1016/s0040-4039(01)91410-8

  日期：1984.1

  Complementary asymmetric alkylation reaction of the lithioenamine derived from 2-methoxycarbonylcyclohexanone and (S)-valine tert-butyl ester was examined by employing the various electron pair donating additives in a toluene solvent, in order to clarify the factors controlling the diastereoface selectivity.

  为了阐明控制非对映异构体选择性的因素，通过在甲苯溶剂中使用各种给电子对添加剂，研究了衍生自2-甲氧基羰基环己酮和（S）-缬氨酸叔丁基酯的硫代亚胺的互补不对称烷基化反应。
• Asymmetric synthesis of tanshindiol A.
  作者：Junning Lee、Jiahe Li、Shunichi Oya、John K. Snyder

  DOI：10.1021/jo00046a009

  日期：1992.9

  The ultrasound-promoted Diels-Alder reaction of 3-methyl-4,5-benzofurandione (10) with appropriately substituted vinylcyclohexenes has led to the synthesis of tanshindiol A (9), a minor component of the Chinese traditional medicine, Dan Shen, prepared from the roots of Salvia miltiorrhiza Bunge. The regioselectivity of the cycloaddition was enhanced by the ultrasonication and was also strongly influenced by the solvent. The asymmetric synthesis of (+)-(4R)-tanshindiol A [(+)-(4R)-91, the naturally occurring enantiomer, proceeded from the optically enriched methyl 6-(benzoyloxy)-1-vinylcyclohexene-6-carboxylate [(-)-(R)-15] or 6-hydroxy-6-(hydroxymethyl)-l-vinylcyclohexene acetonide [(+)-(R)-291 (both 92% ee). Enantioselectivity in the preparation of these diene systems was accomplished by the benzoyl peroxide quench of the lithioenamine derived from methyl 1-oxocyclohexane-2-carboxylate and (S)-valine tert-butyl ester. This procedure, adapted from Koga's asymmetric alkylation of alpha-alkyl beta-keto esters, proved highly effective in preparing the necessary tertiary alcohol in protected form and with high optical purity.