(S)-4-difluoromethylene-2-hydroxymethyl-1-(4-methylbenzenesulfonyl)pyrrolidine | 916843-52-2

• 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: (S)-4-difluoromethylene-2-hydroxymethyl-1-(4-methylbenzenesulfonyl)pyrrolidine
• 英文别名: [(2S)-4-(difluoromethylidene)-1-(4-methylphenyl)sulfonylpyrrolidin-2-yl]methanol
• CAS: 916843-52-2
• 化学式: C₁₃H₁₅F₂NO₃S
• 分子量: 303.33
• InChiKey: ZVTCHMZTWDCNOF-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  66
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (S)-4-difluoromethylene-2-hydroxymethyl-1-(4-methylbenzenesulfonyl)pyrrolidine 在 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium chlorite 作用下， 以 phosphate buffer 、 乙腈 为溶剂， 反应 168.0h， 以93%的产率得到(S)-4-difluoromethylene-1-(4-methylbenzenesulfonyl)proline
  参考文献：
  名称：

  Divergent Chemical Synthesis of Prolines Bearing Fluorinated One-Carbon Units at the 4-Position via Nucleophilic 5-Endo-Trig Cyclizations

  摘要：

  N-[3-(Trifluoromethyl)homoallyl]sulfonamides, prepared via ring opening of (S)-glycidyl ethers or 2-aryloxiranes with 1-(trifluoromethyl)vinyllithium, underwent intramolecular addition or S(N)2'-type reaction in the normally disfavored 5-endo-trig fashion, leading to 2-substituted 4-(trifluoromethyl)- or 4-(difluoromethylene)pyrrolidines. Both alpha- and beta-face-selective hydrogenation of the 4-difluoromethylene group afforded syn- and anti-4-(difluoromethyl)pyrrolidines, respectively. These sequences, followed by the oxidation of a 2-hydroxymethyl or 2-aryl group, successfully provided prolines with a trifluoromethyl, difluoromethylene, or difluoromethyl group at the 4-position, including optically active prolines.

  DOI：

  10.1021/jo061421n
• 作为产物：
  描述：

  (S)-allyl N-[1-(4-methoxybenzyloxy)-4-(trifluoromethyl)pent-4-en-2-yl]-N-(4-methylbenzenesulfonyl)carbamate 在 四(三苯基膦)钯 哌啶 、 sodium hydride 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， 反应 53.5h， 生成 (S)-4-difluoromethylene-2-hydroxymethyl-1-(4-methylbenzenesulfonyl)pyrrolidine
  参考文献：
  名称：

  Divergent Chemical Synthesis of Prolines Bearing Fluorinated One-Carbon Units at the 4-Position via Nucleophilic 5-Endo-Trig Cyclizations

  摘要：

  N-[3-(Trifluoromethyl)homoallyl]sulfonamides, prepared via ring opening of (S)-glycidyl ethers or 2-aryloxiranes with 1-(trifluoromethyl)vinyllithium, underwent intramolecular addition or S(N)2'-type reaction in the normally disfavored 5-endo-trig fashion, leading to 2-substituted 4-(trifluoromethyl)- or 4-(difluoromethylene)pyrrolidines. Both alpha- and beta-face-selective hydrogenation of the 4-difluoromethylene group afforded syn- and anti-4-(difluoromethyl)pyrrolidines, respectively. These sequences, followed by the oxidation of a 2-hydroxymethyl or 2-aryl group, successfully provided prolines with a trifluoromethyl, difluoromethylene, or difluoromethyl group at the 4-position, including optically active prolines.

  DOI：

  10.1021/jo061421n

文献信息

• Divergent Chemical Synthesis of Prolines Bearing Fluorinated One-Carbon Units at the 4-Position via Nucleophilic 5-<i>Endo-Trig</i> Cyclizations
  作者：Ryo Nadano、Yu Iwai、Takashi Mori、Junji Ichikawa

  DOI：10.1021/jo061421n

  日期：2006.11.1

  N-[3-(Trifluoromethyl)homoallyl]sulfonamides, prepared via ring opening of (S)-glycidyl ethers or 2-aryloxiranes with 1-(trifluoromethyl)vinyllithium, underwent intramolecular addition or S(N)2'-type reaction in the normally disfavored 5-endo-trig fashion, leading to 2-substituted 4-(trifluoromethyl)- or 4-(difluoromethylene)pyrrolidines. Both alpha- and beta-face-selective hydrogenation of the 4-difluoromethylene group afforded syn- and anti-4-(difluoromethyl)pyrrolidines, respectively. These sequences, followed by the oxidation of a 2-hydroxymethyl or 2-aryl group, successfully provided prolines with a trifluoromethyl, difluoromethylene, or difluoromethyl group at the 4-position, including optically active prolines.