tert-butyl 4-<(benzylamino)methyl>-3-tosyl-4-pentenoate | 161423-76-3

• 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: tert-butyl 4-<(benzylamino)methyl>-3-tosyl-4-pentenoate
• 英文别名: tert-butyl 4-[(benzylamino)methyl]-3-(4-methylphenyl)sulfonylpent-4-enoate
• CAS: 161423-76-3
• 化学式: C₂₄H₃₁NO₄S
• 分子量: 429.58
• InChiKey: CAANDYLPRCPVAJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.22
• 重原子数：
  30.0
• 可旋转键数：
  9.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  72.47
• 氢给体数：
  1.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  tert-butyl 4-<(benzylamino)methyl>-3-tosyl-4-pentenoate 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 生成 (E)-4-(Benzylamino-methyl)-penta-2,4-dienoic acid tert-butyl ester
  参考文献：
  名称：

  Lithiated γ-Tosyl-Substituted Benzylmethallylamine:  New γ-Amino Methallyl Sulfone Anions in Organic Synthesis

  摘要：

  The mono- and dilithiation of benzyl[2-(tosylmethyl)-2-propenyl]amine (9) with n-butyllithium at -78 degrees C leads to the new allyl sulfone monoanion 10a and dianion 10b, respectively. The intermediate 10a reacts regioselectively at the alpha-position with respect to the sulfone group with different electrophilic reagents (deuterium oxide, alkyl halides, propanal, phenyl isocyanate, and electrophilic olefins) to give the corresponding derivatives 11. In the case of ethyl propiolate, double Michael addition took place, and the trans-substituted methylenepyrrolidine 13 was stereoselectively obtained. Dianion 10b also reacts at the nitrogen atom when alkyl halides and ethyl propiolate are used as electrophiles. These intermediates 10 are appropriate dinucleophiles in annelation reactions with dielectrophiles to afford six-, seven-, and eight-membered ring nitrogen heterocycles 20. When 1,3-dichloroacetone, (Z)-1,4-dichloro-2-butene, and epibromohydrin were used as electrophiles the cyclization process was stereoselective. Studies on the configuration and conformation of prepared heterocycles 20 have been carried out by means of H-1 NMR experiments and X-ray analysis, which have been confirmed by Molecular Mechanics calculations. Base-induced dehydrosulfinylation, reductive desulfonylation, and methylenation reactions have been studied with representative derivatives.

  DOI：

  10.1021/jo9602478
• 作为产物：
  描述：

  2-(chloromethyl)-3-tosylpropene 在 N,N-二甲基丙烯基脲 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 24.25h， 生成 tert-butyl 4-<(benzylamino)methyl>-3-tosyl-4-pentenoate
  参考文献：
  名称：

  Lithiated γ-Tosyl-Substituted Benzylmethallylamine:  New γ-Amino Methallyl Sulfone Anions in Organic Synthesis

  摘要：

  The mono- and dilithiation of benzyl[2-(tosylmethyl)-2-propenyl]amine (9) with n-butyllithium at -78 degrees C leads to the new allyl sulfone monoanion 10a and dianion 10b, respectively. The intermediate 10a reacts regioselectively at the alpha-position with respect to the sulfone group with different electrophilic reagents (deuterium oxide, alkyl halides, propanal, phenyl isocyanate, and electrophilic olefins) to give the corresponding derivatives 11. In the case of ethyl propiolate, double Michael addition took place, and the trans-substituted methylenepyrrolidine 13 was stereoselectively obtained. Dianion 10b also reacts at the nitrogen atom when alkyl halides and ethyl propiolate are used as electrophiles. These intermediates 10 are appropriate dinucleophiles in annelation reactions with dielectrophiles to afford six-, seven-, and eight-membered ring nitrogen heterocycles 20. When 1,3-dichloroacetone, (Z)-1,4-dichloro-2-butene, and epibromohydrin were used as electrophiles the cyclization process was stereoselective. Studies on the configuration and conformation of prepared heterocycles 20 have been carried out by means of H-1 NMR experiments and X-ray analysis, which have been confirmed by Molecular Mechanics calculations. Base-induced dehydrosulfinylation, reductive desulfonylation, and methylenation reactions have been studied with representative derivatives.

  DOI：

  10.1021/jo9602478

文献信息

• Mono and dilithiation of benzyl[2-(tosylmethyl)-2-propenyl] amine: New γ-aminated allyl sulfone anions
  作者：Diego A. Alonso、Carmen Nájera

  DOI：10.1016/s0040-4039(00)78519-4

  日期：1994.11

  The mono and dilithiation of benzyl-[2-(tosylmethyl)-2-propenyl]amine (4) with n-butyllithium affords the corresponding allylic anions 5a and 5b, respectively. Monoanion 5a reacts regioselectively at the a-position of the sulfone group with deuterium oxide, alkyl halides, propanal, methyl crotonate and ethyl propiolate. Dianion 5b reacts with alkyl halides and ethyl propiolate also at the nitrogen atom to give in the case of dihalides 6, 7, and 8 member nitrogen-containing heterocycles.