tert-butyl (2S,4R)-4-[(E)-2-methyloxycarbonyl-1-ethenyl]-2-[(E)-2-phenyl-1-ethenylsulfanylmethyl]pyrrolidine-1-carboxylate | 677736-98-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: tert-butyl (2S,4R)-4-[(E)-2-methyloxycarbonyl-1-ethenyl]-2-[(E)-2-phenyl-1-ethenylsulfanylmethyl]pyrrolidine-1-carboxylate
• 英文别名: tert-butyl (2S,4R)-4-[(E)-3-methoxy-3-oxoprop-1-enyl]-2-[[(E)-2-phenylethenyl]sulfanylmethyl]pyrrolidine-1-carboxylate
• CAS: 677736-98-0
• 化学式: C₂₂H₂₉NO₄S
• 分子量: 403.543
• InChiKey: MTRFCDZJFOZYLJ-BXKMQTTBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  81.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  tert-butyl (2S,4R)-4-[(E)-2-methyloxycarbonyl-1-ethenyl]-2-[(E)-2-phenyl-1-ethenylsulfanylmethyl]pyrrolidine-1-carboxylate 在 2,6-二甲基吡啶 、 间氯过氧苯甲酸 、 三氟乙酸酐 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 反应 3.5h， 生成 tert-butyl (2S,4R)-2-formyl-4-[(E)-2-methyloxycarbonyl-1-ethenyl]pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Efficient Stereoselective Alkenylation through a Homolytic Domino Reaction Involving a 1,5 Sulfur-to-Carbon Translocation

  摘要：

  An effective method for cis-stereoselective attachment of functionalized alkenyl appendages to sp3 carbon is reported. This method is based on a free-radical process, involving a sequence of addition-elimination steps, resulting in alkenyl group transposition from divalent sulfur to a prochiral carbon radical. Absolute stereoselectivity is secured since the new carbon-carbon bond is formed in a ring-closure reaction leading to a bridged bicyclic carbon-centered radical intermediate. The latter undergoes beta-scission of the C-S bond, leaving the alkenyl side chain in its predetermined position while releasing a thiyl radical. This thiyl radical is trapped by tri-n-butylstyryltin, affording a (styrylsulfanyl)methyl side chain and a tri-n-butyltin radical that continues the chain. When 2-(alkenylsulfanyl)methyl-4-bromo(or iodo)pyrrolidines were used as starting materials 2,4-cis-disubstituted 4-alkenyl-2-(styrylsulfanyl)methylpyrrolidines were obtained as products (70-90% yield). Tri-n-butylstyryltin was used rather then the more common n-Bu3SnH as tin radicals sources because the latter led predominantly to bridged bicyclic 3-thia-6-azabicyclo[3.2.1]octanes (up to 77% yield). An additional advantage of using tri-n-butylstyryltin derives from the discovery that the resulting styrylsulfide functionality is an excellent synthetic equivalent to the formyl group. Thus, using a Pummerer-type oxidative desulfurization, 4-cis-alkenyl-proline aldehydes were obtained.

  DOI：

  10.1021/ja031766c
• 作为产物：
  描述：

  (E)-1-phenyl-(2-tributylstannyl)ethene 、 (2S,4S)-4-Bromo-2-((E)-2-methoxycarbonyl-vinylsulfanylmethyl)-pyrrolidine-1-carboxylic acid tert-butyl ester 在 1,1'-偶氮(氰基环己烷) 作用下， 以 甲苯 为溶剂， 反应 7.0h， 生成 tert-butyl (2S,4R)-4-[(E)-2-methyloxycarbonyl-1-ethenyl]-2-[(E)-2-phenyl-1-ethenylsulfanylmethyl]pyrrolidine-1-carboxylate 、 tert-butyl (2S,4R)-4-[(E)-2-methyloxycarbonyl-1-ethenyl]-2-[(Z)-2-phenyl-1-ethenylsulfanylmethyl]pyrrolidine-1-carboxylate
  参考文献：
  名称：

  Efficient Stereoselective Alkenylation through a Homolytic Domino Reaction Involving a 1,5 Sulfur-to-Carbon Translocation

  摘要：

  An effective method for cis-stereoselective attachment of functionalized alkenyl appendages to sp3 carbon is reported. This method is based on a free-radical process, involving a sequence of addition-elimination steps, resulting in alkenyl group transposition from divalent sulfur to a prochiral carbon radical. Absolute stereoselectivity is secured since the new carbon-carbon bond is formed in a ring-closure reaction leading to a bridged bicyclic carbon-centered radical intermediate. The latter undergoes beta-scission of the C-S bond, leaving the alkenyl side chain in its predetermined position while releasing a thiyl radical. This thiyl radical is trapped by tri-n-butylstyryltin, affording a (styrylsulfanyl)methyl side chain and a tri-n-butyltin radical that continues the chain. When 2-(alkenylsulfanyl)methyl-4-bromo(or iodo)pyrrolidines were used as starting materials 2,4-cis-disubstituted 4-alkenyl-2-(styrylsulfanyl)methylpyrrolidines were obtained as products (70-90% yield). Tri-n-butylstyryltin was used rather then the more common n-Bu3SnH as tin radicals sources because the latter led predominantly to bridged bicyclic 3-thia-6-azabicyclo[3.2.1]octanes (up to 77% yield). An additional advantage of using tri-n-butylstyryltin derives from the discovery that the resulting styrylsulfide functionality is an excellent synthetic equivalent to the formyl group. Thus, using a Pummerer-type oxidative desulfurization, 4-cis-alkenyl-proline aldehydes were obtained.

  DOI：

  10.1021/ja031766c