(S)-3-methylene-5-phenyl-2-pyrrolidinone | 125216-88-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: (S)-3-methylene-5-phenyl-2-pyrrolidinone
• 英文别名: (S)-3-methylene-5-phenylpyrrolidin-2-one；(5S)-3-methylidene-5-phenylpyrrolidin-2-one
• CAS: 125216-88-8
• 化学式: C₁₁H₁₁NO
• 分子量: 173.214
• InChiKey: DYBMPCLGVBHOOK-JTQLQIEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  (S)-(-)-2-(benzylidene-amino)-2-phenylethanol 在 盐酸 、 氯化亚砜 、 硫酸 、 四丁基硫酸氢铵 、 silica gel 、 甲基磺酰氯 、 三乙胺 作用下， 以 硝基甲烷 为溶剂， 生成 (S)-3-methylene-5-phenyl-2-pyrrolidinone
  参考文献：
  名称：

  Stereocontrolled preparation of chiral secondary α-methylene γ-lactams by addition of organozinc reagents derived from 2-(bromomethy])acrylates to imines using β-aminoalcohols as chiral auxiliaries.

  摘要：

  Stereocontrolled addition of isolated organozinc reagents 1, prepared from 2-(bromomethyl)acrylates to imines, can be achieved with d.e. approximately 100% using beta-amino alcohols as chiral auxiliaries. High yields of pure R or S secondary alpha-methylene gamma-lactams can be prepared after a three step elimination of the chiral auxiliary (chloration, dehydrochloration of the resulting beta-chloroamine, acid hydrolysis of enamide).

  DOI：

  10.1016/s0957-4166(00)80253-0

文献信息

• Radical carbonylation of ω-alkynylamines leading to α-methylene lactams. Synthetic scope and the mechanistic insights
  作者：Ilhyong Ryu、Takahide Fukuyama、Mami Tojino、Yoshitaka Uenoyama、Yuka Yonamine、Nozomi Terasoma、Hiroshi Matsubara

  DOI：10.1039/c1ob05145h

  日期：——

  carbonyl group of α,β-unsaturated acyl radicals/α-ketenyl radicals via lone pair–π* interaction, which leads to zwitterionic radical species, (ii) the subsequent proton shift from N to O to give hydroxyallyl radicals, (iii) 1,4-hydrogen shift from O to C, and (iv) β-scission to give lactams with liberation of tin radicals. DFT calculations reveal that the 1,4-hydrogen shifts, the key step of the reaction mechanism

  氢化锡介导的自由基羰基化和环化反应以各种ω-炔基胺为底物进行了研究。在该反应中，获得具有五至八元环的α-亚甲基和α-苯乙烯基亚甲基内酰胺作为主要产物。在氮具有能够给出稳定的自由基的取代基如α-苯乙基的情况下，内酰胺环的形成再次通过α-苯乙基的挤出而发生。加上随后的原甲酸酯化程序（TMSCl plus甲醇），这些反应提供了将CO作为内酰胺羰基并入的α-亚甲基内酰胺的有用入口。在胺不具有充当自由基离去基团的取代基的情况下，选择涉及1，4-H转变的反应过程以最终释放锡自由基。因此，所提出的机理涉及（i）胺氮通过以下方式亲核攻击α，β-不饱和酰基/α-烯基的羰基。孤对-π*相互作用，导致两性离子自由基物种；（ii）随后的质子从N转变为O，得到羟基烯丙基自由基；（iii）1,4-氢从O转变为C，以及（iv）β-断定内酰胺释放锡自由基。DFT计算表明，在通常的反应条件下，反应机理的关键步骤是1，4-氢转移。另一方面，产生内酰胺的S
• Catalytic Asymmetric Carbalkoxyallylation of Imines with the Chiral Bis-π-allylpalladium Complex
  作者：Rodney A. Fernandes、Yoshinori Yamamoto

  DOI：10.1021/jo049838l

  日期：2004.5.1

  Carbethoxyallylstannane was employed along with the bis-π-allylpalladium complex to achieve a useful conversion of prochiral imines to chiral 2-(2-aryl-2-aminoethyl)acrylates which are improtant building blocks for further asymmetric synthesis of a wide range of compounds.

  甲乙氧基烯丙基锡烷与双-π-烯丙基钯配合物一起使用，以实现前手性亚胺向手性2-（2-芳基-2-氨基乙基）丙烯酸酯的有用转化，它们是重要的组成部分，用于进一步不对称合成多种化合物。
• Stereoselective Synthesis of α-Methylene-γ-butyrolactams from Ethyl 2-(Bromomethyl)acrylate and Chiral Sulfinyl Aldimines Mediated by Indium
  作者：Miguel Yus、Francisco Foubelo、Haythem K. Dema

  DOI：10.3987/com-09-s(s)27

  日期：——

  The reaction of ethyl 2-(bromomethyl)acrylate (1) with chiral N-tert-butylsulfinyl aldimines 2 and indium powder in THF at 100 degrees C for 48 h affords, after hydrolysis, a mixture of N-tert-butylsulfinyl aminoesters 3 and alpha-methylene-gamma-butyrolactams 4. From the reaction mixture, compounds 3 were quantitatively converted to the expected butyrolactams 4 after removal of the tert-butylsulfinyl group under acidic conditions and final basic workup. The whole process takes place in high overall yields and with fairly good stereoselectivities.
• Enantioselective Synthesis of α-Methylene-γ-butyrolactams Using N-tert-Butanesulfinamides
  作者：Miguel Yus、Francisco Foubelo、Haythem K. Dema

  DOI：10.3987/com-10-s(e)94

  日期：——

  Indium-mediated coupling of ethyl 2-(bromomethyl)acrylate (1) and chiral N-tert-butanelsulfinylimines 2 in a saturated sodium bromide aqueous solution leads to N-tert-butanesulfinyl aminoesters 3 in high yields and diastereoselectivities. After column chromatography purification, enantiomerically pure aminoesters 3 were converted into the expected alpha-methylene-gamma-butyrolactams 4 in a one-pot process.
• LIENNE, M.;MACAUDIERE, P.;CAUDE, M.;ROSSET, R.;TAMRUTE, A., CHIRALITY, 1,(1989) N, C. 45-56
  作者：LIENNE, M.、MACAUDIERE, P.、CAUDE, M.、ROSSET, R.、TAMRUTE, A.

  DOI：——

  日期：——