(Z)-1-butenyl N,N-diisopropylcarbamate | 678150-51-1

• 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: (Z)-1-butenyl N,N-diisopropylcarbamate
• 英文别名: Wkcjslhsxiptnm-fplpwbnlsa-；[(Z)-but-1-enyl] N,N-di(propan-2-yl)carbamate
• CAS: 678150-51-1
• 化学式: C₁₁H₂₁NO₂
• 分子量: 199.293
• InChiKey: WKCJSLHSXIPTNM-FPLPWBNLSA-N

物化性质

• 沸点：
  254.9±13.0 °C(Predicted)
• 密度：
  0.926±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-1-butenyl N,N-diisopropylcarbamate 在 正丁基锂 、 四甲基乙二胺 作用下， 以 四氢呋喃 、 正己烷 、 甲苯 为溶剂， 反应 19.92h， 生成 (2E,4Z)-6-phenylhepta-2,4-dien-4-yl N,N-diisopropylcarbamate
  参考文献：
  名称：

  Asymmetric γ-Deprotonation and Homoaldol Reaction of 1,3-Dien-2-yl Carbamates:  Stereo- and Regiochemistry

  摘要：

  [GRAPHICS]Lithium compounds 7 are configurationally stable intermediates obtained by deprotonation of 1,3-dien-2-yl carbamates 6 with n-butyllithium/(-)-sparteine with a high degree of enantiotopic differentiation at the gamma-position. They react with electrophiles regioselectively giving highly enantioenriched products. Starting with different isomers or changing the double-bond geometries in 6 leads to either of the enantiomers.

  DOI：

  10.1021/ol061005p
• 作为产物：
  描述：

  (E)-but-2-enyl N,N-diisopropylcarbamate 在 正丁基锂 、 四甲基乙二胺 、 titanium(IV) isopropylate 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 1.0h， 以91%的产率得到(Z)-1-butenyl N,N-diisopropylcarbamate
  参考文献：
  名称：

  Highly Enantioenriched Homoenolate Reagents by Asymmetric γ-Deprotonation of Achiral 1-Silyl-Substituted 1-Alkenyl Carbamates

  摘要：

  1-Trimethylsilyl-1-alkenyl carbamates 1 are deprotonated by n-butyllithium/(-)-sparteine (2) with a high degree of enantiotopic differentiation in the gamma-position to form the enantiomerically enriched allyllithium derivatives 3. Trapping these with several electrophiles proceeds stereospecifically in an anti-S-E' or syn-S-E' substitution to form products 4 or ent-4, respectively. Compounds 3a (R = Me) and 3b (R = Ph) exhibit toward carbonyl electrophiles opposite senses of almost complete stereospecificity, thus for 3b(.)2 the involvement of a eta(3)-complex is suggested.

  DOI：

  10.1021/ol0364677

文献信息

• Asymmetric Synthesis of 3,4-Annulated Cyclopentenones from Cycloalkenyl Ketones and Vinyl Carbamates by Diastereoselective Carbonyl Addition/Conrotatory 4π Ring Closure
  作者：Dieter Hoppe、Michael Siemer、Roland Fröhlich

  DOI：10.1055/s-2008-1067150

  日期：2008.7

  1-Lithiated O-vinyl carbamates add with high induced diastereoselectivity onto enantiomerically pure cycloalk-1-enyl (1-dibenzylamino)alkyl ketones. Subsequent O-carbamoyl migration, followed by a torquoselective, antarafacial 4π ring closure, leads to homochiral 2-substituted bicyclo[n.3.0]alk-1-ene-2-ones.

  1-锂化O-乙烯基氨基甲酸酯以高诱导的非对映选择性与对映体纯的环烯烃(1-二苯基氨基)烷基酮发生反应。随后，O-氨基甲酰迁移，再经过扭转选择性的反面4π环闭合，生成同手性的2-取代双环[n.3.0]烷-1-烯-2-酮。
• Enantioselective γ-Deprotonation of Alkyl-SubstitutedO-1,3-Butadien-2-yl Carbamates and Regioselective Asymmetric Homoaldol Reaction
  作者：Roland Bou Chedid、Roland Fröhlich、Birgit Wibbeling、Dieter Hoppe

  DOI：10.1002/ejoc.200700131

  日期：2007.7

  This work presents a facile method for the construction of geometrically defined 1,3-dien-2-yl carbamates. Their highly stereoselective asymmetric deprotonation with the chiral base pair n-butyllithium/(–)-sparteine (2) and substitution reactions allows the flexible synthesis of substituted stereohomogeneous 1,3-dienes. Diastereo- and enantioselective homoaldol reactions with aldehydes are possible

  这项工作提出了一种构建几何定义的 1,3-二烯-2-基氨基甲酸酯的简便方法。它们与手性碱基对正丁基锂/(-)-sparteine (2) 的高度立体选择性不对称去质子化和取代反应允许灵活合成取代的立体均质 1,3-二烯。在锂物质与 ClTi(NEt2)3 进行金属转移后，可以与醛发生非对映选择性和对映选择性高羟醛反应。还介绍了对每种氨基甲酸酯反应的立体化学结果的解释的深入研究。所有结果的比较显示了烯丙基锂中间体的共同性质以及令人惊讶的差异，这表明这些中间体的结构与其反应性之间存在很强的关系。(© Wiley-VCH Verlag GmbH & Co.
• Stereo- and Regiochemical Divergence in the Substitution of a Lithiated Alk-1-en-3-yn-2-yl Carbamate: Synthesis of Highly Enantioenriched Vinylallenes or Alk-3-en-5-yn-1-ols
  作者：Roland Bou Chedid、Michael Brümmer、Birgit Wibbeling、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/anie.200604978

  日期：2007.4.20
• Highly Enantioenriched Homoenolate Reagents by Asymmetric γ-Deprotonation of Achiral 1-Silyl-Substituted 1-Alkenyl Carbamates
  作者：Jenny Reuber、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/ol0364677

  日期：2004.3.1

  1-Trimethylsilyl-1-alkenyl carbamates 1 are deprotonated by n-butyllithium/(-)-sparteine (2) with a high degree of enantiotopic differentiation in the gamma-position to form the enantiomerically enriched allyllithium derivatives 3. Trapping these with several electrophiles proceeds stereospecifically in an anti-S-E' or syn-S-E' substitution to form products 4 or ent-4, respectively. Compounds 3a (R = Me) and 3b (R = Ph) exhibit toward carbonyl electrophiles opposite senses of almost complete stereospecificity, thus for 3b(.)2 the involvement of a eta(3)-complex is suggested.
• Asymmetric γ-Deprotonation and Homoaldol Reaction of 1,3-Dien-2-yl Carbamates:  Stereo- and Regiochemistry
  作者：Roland Bou Chedid、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/ol061005p

  日期：2006.7.1

  [GRAPHICS]Lithium compounds 7 are configurationally stable intermediates obtained by deprotonation of 1,3-dien-2-yl carbamates 6 with n-butyllithium/(-)-sparteine with a high degree of enantiotopic differentiation at the gamma-position. They react with electrophiles regioselectively giving highly enantioenriched products. Starting with different isomers or changing the double-bond geometries in 6 leads to either of the enantiomers.

表征谱图