3,3-Dimethyl-4-(phenylseleno)pyrrolidin-2-one

• 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: 3,3-Dimethyl-4-(phenylseleno)pyrrolidin-2-one
• 英文别名: 3,3-Dimethyl-4-phenylselanylpyrrolidin-2-one；3,3-dimethyl-4-phenylselanylpyrrolidin-2-one
• 化学式: C₁₂H₁₅NOSe
• 分子量: 268.217
• InChiKey: ROMKYGBQFVRZGY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.96
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  methyl 2,2-dimethylbut-3-enoate 在 sodium azide 、 碘苯二乙酸 、 silica gel 、 三苯基膦 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 12.5h， 生成 3,3-Dimethyl-4-(phenylseleno)pyrrolidin-2-one
  参考文献：
  名称：

  Synthesis of nitrogen-containing heterocycles from the azido-selenenylation products of unsaturated carbonyl compounds

  摘要：

  Terminal alkenes containing a remote carbonyl group reacted with iodobenzene diacetate, diphenyl diselenide, and sodium azide to afford the products of azido-phenylselenenylation of the double bond. Owing to its radical nature, this reaction proceeded with complete anti-Markovnikov regioselectivity. Under the influence of triphenylphosphine in benzene the azido group reacted with the carbonyl function to afford the corresponding ring-closure reaction products containing a carbon nitrogen double bond. Thus, starting from beta,gamma- or gamma,delta-unsaturated esters, the corresponding cyclic imino ethers were obtained. These could not be isolated but were directly transformed into beta-(phenylseleno) gamma-lactams or gamma-(phenylseleno) delta-lactams. The phenylseleno derivatives of tetrahydropyridine were formed starting both from gamma,delta-unsaturated ketones and from alpha-allyl beta-keto esters. In the latter case, the cyclization reaction is chemoselective and involves the ketonic carbonyl. The oxidation of these compounds with hydrogen peroxide directly produced the corresponding pyridines via selenoxide elimination followed by dehydrogenation. This simple reaction sequence represents a very useful general method to build up a 2-substituted pyridine ring. Several alkyl-, aryl-, and heteroarylpyridines, bipyridines, and a terpyridine have been prepared.

  DOI：

  10.1021/jo00074a042

文献信息

• Synthesis of nitrogen-containing heterocycles from the azido-selenenylation products of unsaturated carbonyl compounds
  作者：Marco Tingoli、Marcello Tiecco、Lorenzo Testaferri、Roberto Andrenacci、Roberta Balducci

  DOI：10.1021/jo00074a042

  日期：1993.10

  Terminal alkenes containing a remote carbonyl group reacted with iodobenzene diacetate, diphenyl diselenide, and sodium azide to afford the products of azido-phenylselenenylation of the double bond. Owing to its radical nature, this reaction proceeded with complete anti-Markovnikov regioselectivity. Under the influence of triphenylphosphine in benzene the azido group reacted with the carbonyl function to afford the corresponding ring-closure reaction products containing a carbon nitrogen double bond. Thus, starting from beta,gamma- or gamma,delta-unsaturated esters, the corresponding cyclic imino ethers were obtained. These could not be isolated but were directly transformed into beta-(phenylseleno) gamma-lactams or gamma-(phenylseleno) delta-lactams. The phenylseleno derivatives of tetrahydropyridine were formed starting both from gamma,delta-unsaturated ketones and from alpha-allyl beta-keto esters. In the latter case, the cyclization reaction is chemoselective and involves the ketonic carbonyl. The oxidation of these compounds with hydrogen peroxide directly produced the corresponding pyridines via selenoxide elimination followed by dehydrogenation. This simple reaction sequence represents a very useful general method to build up a 2-substituted pyridine ring. Several alkyl-, aryl-, and heteroarylpyridines, bipyridines, and a terpyridine have been prepared.