(1S)-2-ethoxy-1-methyl-2-oxoethyl 3-oxobutanoate | 22886-02-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: (1S)-2-ethoxy-1-methyl-2-oxoethyl 3-oxobutanoate
• 英文别名: (2S)-1-ethoxy-1-oxopropan-2-yl 3-oxobutanoate；(S)-(1-ethoxycarbonyl-ethyl)-acetoacetate；ethyl (S)-(-)-lactate acetoacetate；(S)-α-(Acetoacetoxy)-propionsaeureethylester；[(2S)-1-ethoxy-1-oxopropan-2-yl] 3-oxobutanoate
• CAS: 22886-02-8
• 化学式: C₉H₁₄O₅
• 分子量: 202.207
• InChiKey: BTCYFWDWPKLJCC-ZETCQYMHSA-N

物化性质

• 沸点：
  274.0±15.0 °C(Predicted)
• 密度：
  1.113±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  14
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  69.7
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (1S)-2-ethoxy-1-methyl-2-oxoethyl 3-oxobutanoate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 生成 2-Diazo-3-oxo-butyric acid (S)-1-ethoxycarbonyl-ethyl ester
  参考文献：
  名称：

  高度官能化的 8-氧杂双环 [3.2.1] 辛烯衍生物的不对称合成

  摘要：

  在呋喃的存在下，羧酸铑 (II) 催化乙烯基重氮甲烷的分解导致一般合成氧杂双环 [3.2.1] octa-2,6-二烯衍生物。这些氧双环产品是有机合成中的通用中间体。[3 + 4] 环化的机制被认为是串联环丙烷化/Cope 重排。这种机制与在这些 [3 + 4] 环中观察到的出色的区域和立体控制是一致的。通过使用铑（II）（S）-N-（叔丁基苯）磺酰基脯氨酸盐作为催化剂或使用（S）-乳酸盐或（R）-泛内酯作为类卡宾的手性助剂，可以不对称合成氧杂双环产物。

  DOI：

  10.1021/ja962081y
• 作为产物：
  描述：

  双乙烯酮 、 L(-)-乳酸乙酯 在 吡啶 作用下， 以 苯 为溶剂， 生成 (1S)-2-ethoxy-1-methyl-2-oxoethyl 3-oxobutanoate
  参考文献：
  名称：

  高度官能化的 8-氧杂双环 [3.2.1] 辛烯衍生物的不对称合成

  摘要：

  在呋喃的存在下，羧酸铑 (II) 催化乙烯基重氮甲烷的分解导致一般合成氧杂双环 [3.2.1] octa-2,6-二烯衍生物。这些氧双环产品是有机合成中的通用中间体。[3 + 4] 环化的机制被认为是串联环丙烷化/Cope 重排。这种机制与在这些 [3 + 4] 环中观察到的出色的区域和立体控制是一致的。通过使用铑（II）（S）-N-（叔丁基苯）磺酰基脯氨酸盐作为催化剂或使用（S）-乳酸盐或（R）-泛内酯作为类卡宾的手性助剂，可以不对称合成氧杂双环产物。

  DOI：

  10.1021/ja962081y

文献信息

• The Use of Magnesium Nitride for the Synthesis of Enantiomerically Pure 1,4-Dihydropyridines via the Hantzsch Reaction
  作者：Mauro Panunzio、Zhining Xia、Sha Long、Alessandra Petroli、Wenling Qin

  DOI：10.1055/s-0030-1258462

  日期：2011.4

  Enantiomerically pure 1,4-dihydropyridines are prepared taking advantage of magnesium nitride as a useful and convenient source of ‘solid ammonia’. The products possess various substituents at carbons 3, 4 and 5 of the dihydropyridine moiety.

  利用氮化镁这一有用的“固态氨”来源，制备了高光学纯度的1,4-二氢吡啶。产物在二氢吡啶部分的3、4和5位碳上具有多种取代基。
• Development of methods for the synthesis of chiral, highly functionalized 2-amino-4-aryl-4H-pyrans
  作者：José L. Marco、Nazario Martín、Angeles Martínez-Grau、Carlos Seoane、Armando Albert、Félix H. Cano

  DOI：10.1016/s0040-4020(01)87029-0

  日期：1994.3

  The development of new methods for the asymmetric synthesis of highly functionalized 2-amino-4-aryl-4H-pyrans is described. Two alternative synthetic routes: the 1,4-conjugate addition of chiral β-ketoesters 3 or the N-acetoacetyl sultam 11 to arylidenemalononitriles 6, and the Michael addition of malononitrile to enantiomerically pure α-acetylcinnamates 5, have been designed. Depending upon the chiral

  描述了不对称合成高度官能化的2-氨基-4-芳基-4 H-吡喃的新方法的开发。两个替代的合成路线：1,4-共轭加成的手性β酮酯的3或Ñ -acetoacetyl磺内酰胺11至arylidenemalononitriles 6，并且迈克尔加成丙二腈对映异构体纯α-acetylcinnamates 5，已经设计。取决于手性助剂，以低[（-）-薄荷醇，（-）-冰片，（-）-乳酸乙酯]至良好（Oppolzer's sultam）非对映异构体过量得到所得的4 H-吡喃。化合物12a的次要异构体中新立体中心的绝对构型通过X射线衍射分析确定为S。用氢化铝锂对4 H-吡喃12进行的还原裂解得到对映体纯的或富集的醇14。
• Process for producing optically pure 1,4-dihydropyridines
  申请人：Laboratoire L. Lafon

  公开号：US05633383A1

  公开（公告）日：1997-05-27

  The invention relates to a process which comprises the crystallization of a calcium salt of chiral (R or S) lactic acid esterified with a racemic dihydropyridine.

  该发明涉及一种过程，其中包括结晶由光学异构体（R或S）乳酸酯化的钙盐和外消旋二氢吡啶。
• Enantioselective Synthesis of Functionalized Tropanes by Rhodium(II) Carboxylate-Catalyzed Decomposition of Vinyldiazomethanes in the Presence of Pyrroles
  作者：Huw M. L. Davies、Julius J. Matasi、L. Mark Hodges、Nicholas J. S. Huby、Craig Thornley、Norman Kong、Jeffrey H. Houser

  DOI：10.1021/jo961920w

  日期：1997.2.1

  A series of enantiomerically enriched tropanes was synthesized by the rhodium(II) octanoate-catalyzed reaction of various N-BOC-protected pyrroles with vinyldiazomethanes. The overall 3 + 4 annulation occurs by a tandem cyclopropanation/Cope rearrangement. Asymmetric induction was best achieved in these transformations by using either (S)-lactate or (R)-pantolactone as a chiral auxiliary on the vinyldiazomethanes. Reactions carried out with the chiral catalyst tetrakis[N-( 4-tert-butylbenzenesulfonyl)-(L)-prolinato]dirhodium (2) provided moderate asymmetric induction, but also resulted in the formation of isomeric azabicyclooctane side products. The utility of the synthetic process was demonstrated through the asymmetric synthesis of(-)-anhydroecgonine methyl ester and (-)-ferruginine.
• Calcium- and calmodulin-antagonism of elnadipine derivatives: comparative SAR
  作者：R Mannhold、B Jablonka、W Voigt、K Schönafinger、E Schraven

  DOI：10.1016/0223-5234(92)90006-m

  日期：1992.4

  The Ca2+-antagonistic properties of elnadipine derivatives have been quantified by means of binding experiments in bovine cerebral cortex membranes using H-3-nitrendipine. Competition experiments have shown a 308-fold concentration range of K(i)-values (2.9 x 10(-10) to 8.9 x 10(-8)) for elnadipine derivatives and a eudismic ratio for elnadipine and its (+)-enantiomer of 448. Calmodulin (CaM)-antagonistic properties have been measured in the test system of CaM-stimulated phosphodiesterase. The concentration range of IC50 values only amounts to 9 (5 x 10(-7) to 4.5 x 10(-6) M). In contrast to Ca2+-antagonism, enantioselectivity of CaM-inhibition by elnadipine is negligible. CaM-antagonistic potency of elnadipine derivatives is diminished by a factor of 10 to 5000 as compared to their Ca2+-antagonistic potency. The following conclusions regarding structural determinants of Ca2+- and CaM-antagonistic properties can be made: lipophilic substituents of the oxadiazole in 5-position of the dihydropyridine (DHP) ring increase the CaM-antagonistic and decrease the Ca2+-antagonistic potency: correspondingly the unsubstituted compound is the strongest Ca2+- and the weakest CaM-antagonist; 1,3,4-oxadiazole substitution is superior to 1,2,4-oxadiazole as regards Ca2+- and CaM-antagonistic potency.