Methyl (2E,4R,5S)-6-methyl-4,5-[N-(2,4,6-trimethylphenylsulfonyl)epimino]hept-2-enoate | 189291-16-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Methyl (2E,4R,5S)-6-methyl-4,5-[N-(2,4,6-trimethylphenylsulfonyl)epimino]hept-2-enoate
• 英文别名: methyl (E)-3-[(2R,3S)-3-propan-2-yl-1-(2,4,6-trimethylphenyl)sulfonylaziridin-2-yl]prop-2-enoate
• CAS: 189291-16-5
• 化学式: C₁₈H₂₅NO₄S
• 分子量: 351.467
• InChiKey: RYEIFGVYCAYLLM-WQOVDVSISA-N

物化性质

• 熔点：
  78 °C
• 沸点：
  466.1±55.0 °C(Predicted)
• 密度：
  1.218±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  71.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Methyl (2E,4R,5S)-6-methyl-4,5-[N-(2,4,6-trimethylphenylsulfonyl)epimino]hept-2-enoate 以 氯仿 为溶剂， 反应 15.0h， 生成 (E)-(4S,5S)-4-Hydroxy-6-methyl-5-(2,4,6-trimethyl-benzenesulfonylamino)-hept-2-enoic acid methyl ester
  参考文献：
  名称：

  Regiospecific ring-opening reactions of β-aziridinyl α,β-enoates with acids: application to the stereoselective synthesis of a couple of diastereoisomeric (E )-alkene dipeptide isosteres from a single β-aziridinyl α,β-enoate and to the convenient preparation of amino alcohols bearing α,β-unsaturated ester groups

  摘要：

  已经发现N-(2,4,6-三甲基苯磺酰)-γ,δ-cis-或-trans-γ,δ-表胺(E)-α,β-烯酸酯与酸如甲磺酸(MSA)或三氟乙酸(TFA)的区域和立体选择性开环反应。这些开环反应对于使用γ,δ-表胺(E)-α,β-烯酸酯单一底物合成一对非对映体(E)-烯二肽同分异构体，以及方便制备δ-氨基γ-羟基α,β-烯酸酯具有重要意义。

  DOI：

  10.1039/a904671b
• 作为产物：
  描述：

  (E)-(4S,5S)-6-Methyl-4-(2,2,2-trifluoro-acetoxy)-5-(2,4,6-trimethyl-benzenesulfonylamino)-hept-2-enoic acid methyl ester 在 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.5h， 生成 Methyl (2E,4R,5S)-6-methyl-4,5-[N-(2,4,6-trimethylphenylsulfonyl)epimino]hept-2-enoate
  参考文献：
  名称：

  Regiospecific ring-opening reactions of β-aziridinyl α,β-enoates with acids: application to the stereoselective synthesis of a couple of diastereoisomeric (E )-alkene dipeptide isosteres from a single β-aziridinyl α,β-enoate and to the convenient preparation of amino alcohols bearing α,β-unsaturated ester groups

  摘要：

  已经发现N-(2,4,6-三甲基苯磺酰)-γ,δ-cis-或-trans-γ,δ-表胺(E)-α,β-烯酸酯与酸如甲磺酸(MSA)或三氟乙酸(TFA)的区域和立体选择性开环反应。这些开环反应对于使用γ,δ-表胺(E)-α,β-烯酸酯单一底物合成一对非对映体(E)-烯二肽同分异构体，以及方便制备δ-氨基γ-羟基α,β-烯酸酯具有重要意义。

  DOI：

  10.1039/a904671b

文献信息

• Palladium(0)-Catalyzed Isomerization Reactions of Aziridines Bearing an α,β-Unsaturated Ester Group:  A Thermodynamic Preference for Chiral Alkyl (2<i>E</i>)-4,5-<i>cis</i>-4,5-Epimino-<i>N</i>-(alkyl- or arylsulfonyl) 2-Enoates over the Other Three Stereoisomers
  作者：Toshiro Ibuka、Norio Mimura、Hiroaki Ohno、Kazuo Nakai、Masako Akaji、Hiromu Habashita、Hirokazu Tamamura、Yoshihisa Miwa、Tooru Taga、Nobutaka Fujii、Yoshinori Yamamoto

  DOI：10.1021/jo962094u

  日期：1997.5.1

  Palladium(0)-catalyzed reactions of five sets of four stereoisomeric 4,5-epimino-N-(methanesulfonyl) or -N-(arylsulfonyl) 2-enoates reveal that 4,5-cis-(2E)-isomers are thermodynamically more stable than other isomers, in accord with calculations. A highly stereoselective synthesis of (E)-alkene dipeptide isosteres having the desired stereochemistries from unwanted stereoisomeric 4,5-epimino-N-(arylsulfonyl)

  钯（0）催化的五组四个四个立体异构体4,5-表氨-N-（甲磺酰基）或-N-（芳基磺酰基）2-烯酸酯的反应表明，4,5-顺式（（2E））异构体的热力学性质更高根据计算，该化合物比其他异构体稳定。还提出了由不想要的立体异构体4，5-表观氨基-N-（芳基磺酰基）2-烯酸酯的具有所需立体化学的（E）-烯烃二肽等排物的高度立体选择性合成。
• A thermodynamic preference of chiral cis-γ,δ-epimino-(E)-α,β-unsaturated esters over other stereoisomers: Synthetically useful Pd(0)-catalyzed equilibrated reactions of aziridines bearing an α,β-unsaturated ester group
  作者：Toshiro Ibuka、Masako Akaji、Norio Mimura、Hiromu Habashita、Kazuo Nakai、Hirokazu Tamamura、Nobutaka Fujii、Yoshinori Yamamoto

  DOI：10.1016/0040-4039(96)00403-0

  日期：1996.4

  A practical synthesis of chiral N-arylsulfonyl-cis-γ,δ-epimino-(E)-α,β-enoates, key intermediates for the synthesis of (E)-alkene dipeptide isosteres via Pd(0)-catalyzed equilibrated reactions, has been successfully achieved by exposing N-arylsulfonyl-γ,δ-epimino-α,β-unsaturated esters to a catalytic amount of Pd(PPh3)4 in THF at 0 ∼ 20 °C.

  手性的实用合成Ñ -arylsulfonyl-顺- γ，δ -epimino-（ë） - α，β -enoates，对（合成关键中间体ë） -烯烃电子等排体的二肽通过钯（0）催化的平衡反应，通过将N-芳基磺酰基-γ，δ-表-氨基-α，β-不饱和酯暴露于催化量的Pd（PPh 3）4在THF中的温度为0到20°C，可以成功地实现这一目的。
• Stereoselective synthesis of a set of two functionalized (E)-alkene dipeptide isosteres of L-amino acid-L-Glu and L-amino acid-D-Glu
  作者：Shinya Oishi、Hirokazu Tamamura、Masaki Yamashita、Yoshihiko Odagaki、Nobuyuki Hamanaka、Akira Otaka、Nobutaka Fujii

  DOI：10.1039/b103833h

  日期：——

  Treatment of N-arylsulfonyl-γ,δ-cis- or -trans-γ,δ-epimino (E)-α,β-enoates with HCl–1,4-dioxane affords regio- and stereo-selective ring-opened products, δ-aminated γ-chloro-α,β-enoates. This ring-opening reaction provides a useful method for the stereoselective synthesis of a set of diastereomeric (L-Xaa, L-Glu)-type and (L-Xaa, D-Glu)-type (E)-alkene dipeptide isosteres (EADIs) from a single substrate of γ,δ-epimino (E)-α,β-enoate using organozinc–copper reagents.

  N-arylsulfonyl-γ,δ-cis- or -trans-γ,δ-epimino (E)-α,β-烯酸盐用 HCl-1,4- 二氧六环处理后，可得到具有区域和立体选择性的开环产物--δ-氨基 γ-氯-α,β-烯酸盐。这种开环反应为使用有机锌铜试剂从单一底物γ,δ-表亚胺 (E)-α,β-烯酸盐立体选择性合成一组非对映异构体 (L-Xaa, L-Glu) 型和 (L-Xaa, D-Glu) 型 (E)- 烯二肽异构体 (EADIs) 提供了一种有用的方法。
• Regiospecific ring-opening reactions of aziridines bearing an α,β-unsaturated ester group with trifluoroacetic acid or methanesulfonic acid: application to the stereoselective synthesis of (E)-alkene dipeptide isosteres
  作者：Hirokazu Tamamura

  DOI：10.1039/a706027k

  日期：——

  Reaction of N-(2,4,6-trimethylphenylsulfonyl)-γ,δ-cis- or -trans-γ,δ-epimino (E)-α,β-enoates with acids such as TFA or methanesulfonic acid (MSA) affords the stereo- and regio-selective ring-opened products in high yields, and subsequent treatment of resulting δ-aminated γ-mesyloxyα,β-enoates with organocopper reagents yields diastereoisomerically pure (E)-alkene dipeptide isosteres.

  N-(2,4,6-三甲基苯磺酰基)-δ³,δ-顺式或反式-δ³,δ-表亚胺 (E)-δ±,δ-烯酸盐与反式脂肪酸或甲磺酸 (MSA) 等酸反应，可获得高产率的立体和区域选择性开环产物、随后用有机铜试剂处理生成的δ-氨基δ-甲酰氧基δ,δ-烯酸盐，可得到非对映异构体纯度很高的（E）-烯二肽异构体。
• Regiospecific ring-opening reactions of β-aziridinyl α,β-enoates with acids: application to the stereoselective synthesis of a couple of diastereoisomeric (E )-alkene dipeptide isosteres from a single β-aziridinyl α,β-enoate and to the convenient preparation of amino alcohols bearing α,β-unsaturated ester groups
  作者：Hirokazu Tamamura、Masaki Yamashita、Yutaka Nakajima、Kyoko Sakano、Akira Otaka、Hiroaki Ohno、Toshiro Ibuka、Nobutaka Fujii

  DOI：10.1039/a904671b

  日期：——

  Regio- and stereo-selective ring-opening reactions of N-(2,4,6-trimethylphenylsulfonyl)-γ,δ-cis- or -trans-γ,δ-epimino (E)-α,β-enoates with acids such as methanesulfonic acid (MSA) or trifluoroacetic acid (TFA) have been found. These ring-opening reactions are useful for the stereoselective synthesis of a couple of diastereomeric (E)-alkene dipeptide isosteres from a single substrate of γ,δ-epimino (E)-α,β-enoate, and for the convenient preparation of δ-aminated γ-hydroxy α,β-enoates.

  已经发现N-(2,4,6-三甲基苯磺酰)-γ,δ-cis-或-trans-γ,δ-表胺(E)-α,β-烯酸酯与酸如甲磺酸(MSA)或三氟乙酸(TFA)的区域和立体选择性开环反应。这些开环反应对于使用γ,δ-表胺(E)-α,β-烯酸酯单一底物合成一对非对映体(E)-烯二肽同分异构体，以及方便制备δ-氨基γ-羟基α,β-烯酸酯具有重要意义。