ethyl (2RS)-3,3-[(1R,2R)-cyclohexane-1,2-dioxy]-2-ethylbutanoate | 501098-20-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (2RS)-3,3-[(1R,2R)-cyclohexane-1,2-dioxy]-2-ethylbutanoate
• 英文别名: ethyl 2-[(3aR,7aR)-2-methyl-3a,4,5,6,7,7a-hexahydro-1,3-benzodioxol-2-yl]butanoate
• CAS: 501098-20-0
• 化学式: C₁₄H₂₄O₄
• 分子量: 256.342
• InChiKey: BNGSNQQGTOTQSK-PQDIPPBSSA-N

物化性质

• 沸点：
  319.3±12.0 °C(Predicted)
• 密度：
  1.040±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  44.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl (2RS)-3,3-[(1R,2R)-cyclohexane-1,2-dioxy]-2-ethylbutanoate 在 盐酸 、 六甲基磷酰三胺 、 sodium azide 、 甲烷磺酸 、 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 氯仿 、 水 为溶剂， 反应 157.5h， 生成 ethyl (S)-α-ethylleucinate
  参考文献：
  名称：

  Conformation of Peptides Containing a Chiral -Ethylated ,-Disubstituted -Amino Acid: (S)--Ethylleucine (=(2S)-2-Amino-2-ethyl-4-methylpentanoic Acid) within Sequences of Dimethylglycine and Diethylglycine Residues

  摘要：

  An optically active (S)-alpha-ethylleucine ((S)-alphaEtLeu) as a chiral alpha-ethylated alpha,alpha-disubstituted alpha-amino acid was synthesized by means of a chiral acetal auxiliary of (R,R)-cyclohexane-1,2-diol. The chiral alpha-ethylated alpha,alpha-disubstituted amino acid (S)-alphaEtLeu was introduced into the peptides constructed from 2aminoisobutyric acid (= dimethylglycine, Aib), and also into the peptide prepared from diethylglycine (Deg). The X-ray crystallographic analysis revealed that both right-handed (P) and left-handed (M) 3(10)-helical structures exist in the solid state of CF3CO-(Aib)(2)-[(S)-alphaEtLeu]-(Aib)(2)-OEt (14) and CF3CO-[(S)-alphaEtLeu]-(Deg)(4)-OEt (18), respectively. The IR, CD, and H-1-NMR spectra indicated that the dominant conformation of pentapeptides 14 and CF3CO-[(S)-alphaEtLeu]-(Aib)(4)-OEt (16) in solution is a 3(10)-helical structure, and that of 18 in solution is a planar C-5 conformation. The conformation of peptides was also studied by molecular-mechanics calculations.

  DOI：

  10.1002/1522-2675(200210)85:10<3197::aid-hlca3197>3.0.co;2-y
• 作为产物：
  描述：

  trans-1,2-cyclohexandiol 在 吡啶 、 Pseudomonas fluorescens Amano P lipase 、 potassium carbonate 、 对甲苯磺酸 作用下， 以 甲醇 、 aq. phosphate buffer 、 水 、 苯 为溶剂， 反应 44.75h， 生成 ethyl (2RS)-3,3-[(1R,2R)-cyclohexane-1,2-dioxy]-2-ethylbutanoate
  参考文献：
  名称：

  光诱导的环化级联反应-（-）-Leuconoxine的总合成

  摘要：

  完成了单萜类吲哚生物碱（-）-leuconoxine的无保护基团和对映选择性总合成。关键步骤包括涉及Witkop环化的新型光诱导的多米诺骨化大环化/环过环化，为此提供了更多的机理证据。该过程提供了二氮杂[5.5.6.6] fenestrane骨架，这是迄今为止前所未有的结构元素。

  DOI：

  10.1002/chem.201500656

文献信息

• An Extended Planar C5 Conformation and a 310-Helical Structure of Peptide Foldamer Composed of Diverse -Ethylated ,-Disubstituted -Amino Acids
  作者：Masakazu Tanaka、Shin Nishimura、Makoto Oba、Yosuke Demizu、Masaaki Kurihara、Hiroshi Suemune

  DOI：10.1002/chem.200204476

  日期：2003.7.7

  active peptide foldamers Tfa-[(S)-(alphaEt)Leu]-[(S)-(alphaEt)Nva]-Deg-[(S)-(alphaEt)Nle]-OEt (10) and Tfa-[(S)-(alphaEt)Val]-[(S)-(alphaEt)Leu]-[(S)-(alphaEt)Nva]-Deg-[(S)-(alphaEt)Nl e]-OEt (11) composed of diverse alpha-ethylated alpha,alpha-disubstituted alpha-amino acids were synthesized. The dominant conformation of these peptides in solution was an unusual, fully extended planar conformation, and

  光学活性肽折叠剂Tfa-[（S）-（alphaEt）Leu]-[（S-（alphaEt）Nva] -Deg-[（S）-（alphaEt）Nle] -OEt（10）和Tfa-[（ S）-（alphaEt）Val]-[（S）-（alphaEt）Leu]-[（S）-（alphaEt）Nva] -Deg-[（S）-（alphaEt）Nle e] -OEt（11）组成合成了多种α-乙基化的α，α-二取代的α-氨基酸。这些肽在溶液中的主要构象是一个不寻常的，完全延伸的平面构象，并且在晶体状态下是右旋（P）和左旋（M）3（10）螺旋结构，其中10和P图11中的3（10）-螺旋结构。由手性α-乙基化的α，α-二取代的α-氨基酸制备的肽的优选平面C（5）构象与由手性α-甲基化的α，制备的肽的3（10）-螺旋结构完全不同，
• Asymmetric Synthesis of α,α-Disubstituted α-Amino Acids Using (<i>S</i>,<i>S</i>)-Cyclohexane-1,2-diol as a Chiral Auxiliary
  作者：Masakazu Tanaka、Makoto Oba、Koichi Tamai、Hiroshi Suemune

  DOI：10.1021/jo001423m

  日期：2001.4.1

  Diastereoselective alkylation of ethyl 2-methyl- and/or 2-ethylacetoacetates using the (S,S)cyclohexane-1,2-diol as an acetal chiral auxiliary afforded enol ethers (2a-f and 5a-f) of 92 - > 95% de in 31-70% yields. Removal of the cyclohexane-l,2-diol with BF3-OEt2 afforded beta -keto esters (3 and 6) bearing a chiral quaternary carbon. The beta -keto esters could be easily converted into optically active alpha -methylated and/or alpha -ethylated alpha,alpha -disubstituted amino acids (12 and 13) in 21-99% yields using Schmidt rearrangement.
• A Photoinduced Cyclization Cascade-Total Synthesis of (−)-Leuconoxine
  作者：Magnus Pfaffenbach、Tanja Gaich

  DOI：10.1002/chem.201500656

  日期：2015.4.20

  enantioselective total synthesis of the monoterpenoid indole alkaloid (−)‐leuconoxine was accomplished. The key step comprises a novel photoinduced domino macrocyclization/transannular cyclization involving the Witkop cyclization, for which additional mechanistic evidence is provided. This process furnishes a diaza[5.5.6.6]fenestrane skeleton, which is a hitherto unprecedented structure element.

  完成了单萜类吲哚生物碱（-）-leuconoxine的无保护基团和对映选择性总合成。关键步骤包括涉及Witkop环化的新型光诱导的多米诺骨化大环化/环过环化，为此提供了更多的机理证据。该过程提供了二氮杂[5.5.6.6] fenestrane骨架，这是迄今为止前所未有的结构元素。
• Conformation of Peptides Containing a Chiral -Ethylated ,-Disubstituted -Amino Acid: (S)--Ethylleucine (=(2S)-2-Amino-2-ethyl-4-methylpentanoic Acid) within Sequences of Dimethylglycine and Diethylglycine Residues
  作者：Makoto Oba、Masakazu Tanaka、Masaaki Kurihara、Hiroshi Suemune

  DOI：10.1002/1522-2675(200210)85:10<3197::aid-hlca3197>3.0.co;2-y

  日期：2002.10

  An optically active (S)-alpha-ethylleucine ((S)-alphaEtLeu) as a chiral alpha-ethylated alpha,alpha-disubstituted alpha-amino acid was synthesized by means of a chiral acetal auxiliary of (R,R)-cyclohexane-1,2-diol. The chiral alpha-ethylated alpha,alpha-disubstituted amino acid (S)-alphaEtLeu was introduced into the peptides constructed from 2aminoisobutyric acid (= dimethylglycine, Aib), and also into the peptide prepared from diethylglycine (Deg). The X-ray crystallographic analysis revealed that both right-handed (P) and left-handed (M) 3(10)-helical structures exist in the solid state of CF3CO-(Aib)(2)-[(S)-alphaEtLeu]-(Aib)(2)-OEt (14) and CF3CO-[(S)-alphaEtLeu]-(Deg)(4)-OEt (18), respectively. The IR, CD, and H-1-NMR spectra indicated that the dominant conformation of pentapeptides 14 and CF3CO-[(S)-alphaEtLeu]-(Aib)(4)-OEt (16) in solution is a 3(10)-helical structure, and that of 18 in solution is a planar C-5 conformation. The conformation of peptides was also studied by molecular-mechanics calculations.