3-[di(methoxycarbonyl)methyl]-2-methyl-3-phenylisoindolin-1-one | 1449378-83-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 异吲哚及其衍生物
• 英文名称: 3-[di(methoxycarbonyl)methyl]-2-methyl-3-phenylisoindolin-1-one
• 英文别名: Dimethyl 2-(2-methyl-3-oxo-1-phenylisoindol-1-yl)propanedioate
• CAS: 1449378-83-9
• 化学式: C₂₀H₁₉NO₅
• 分子量: 353.375
• InChiKey: MCRSLHKGYXVSHD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  26
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  72.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为产物：
  描述：

  甲醇 、 一氧化碳 、 methyl 3-[2-(methylcarbamoyl)phenyl]-3-phenylprop-2-enoate;palladium(2+);N,N,N',N'-tetramethylethane-1,2-diamine;trifluoromethanesulfonate 以 氯仿 为溶剂， 20.0 ℃ 、140.0 kPa 条件下， 反应 6.0h， 以83%的产率得到3-[di(methoxycarbonyl)methyl]-2-methyl-3-phenylisoindolin-1-one
  参考文献：
  名称：

  Reactivity of Ortho-Palladated Benzamides toward CO, Isocyanides, and Alkynes. Synthesis of Functionalized Isoindolin-1-ones and 4,5-Disubstituted Benzo[c]azepine-1,3-diones

  摘要：

  Aryl palladium complexes [Pd{C6H4C(O)NRR'-2}I(tmeda)] [NRR' = NH2 (1a), NHMe (1b), NMe2 (1c); tmeda = N,N,N',N'-tetramethylethylenediamine] are prepared by oxidative addition of the corresponding 2-iodophenylbenzamides to Pd(dba)(2) ([Pd-2(dba)(3)]center dot dba; dba = dibenzylideneacetone) in the presence of tmeda. Cationic cyclometalated derivatives [Pd{'2C,O-C6H4C(O)NRR'-2}(tmeda)]TfO (2ac) are obtained by iodide abstraction from the appropriate complex 1 with AgTfO, while the deprotonation of the amide function of 1a or 1b with KOtBu gives the neutral amidate complexes [Pd{'2C,N-C6H4C(O)NR-2}(tmeda)] [R = H (3a), Me (3b)]. Complexes 2a,b and 3a,b react with CO under mild conditions to yield phthalimide (4a) or N-methylphthalimide (4b), whereas the reactions of derivatives 1c and 2c with CO are very slow and give N-1,N-1,N-2,N-2-tetramethylphthalamide and phthalic anhydride. The reaction of 1b with 1 equiv of XyNC (Xy = 2,6-dimethylphenyl) or tBuNC affords Pd(0), (tmedaH)I, and 3-(2,6-dimethylphenylimino)-2-methylisoindolin-1-one (5b) or 3-(tert-butylimino)-2-methylisoindolin-1-one (5b'), respectively, while complex 1c reacts with 3 equiv of XyNC to give trans-[Pd{C('NXy)C6H4C(O)NMe2-2}I(CNXy)(2)] (6). The seven-membered palladacycles [Pd{'2C,O-C(X)'C(X')C6H4C(O)NRR'-2}(tmeda)]TfO [NRR' = NH2 and X = Ph, X' = Me (7a); NRR' = NHMe and X = Ph, X' = Me (7b), X = X' = Ph (8b), Et (9b), CO2Me (10b), X = CO2Me, X' = Ph (11b), X = CO2Et, X' = Ph (12b); NRR' = NMe2 and X = X' = Ph (8c), Et (9c)] are obtained from the reactions of 2ac with alkynes. Treatment of complexes 7a, 7b, 8b, and 9b with CO at room temperature gives the corresponding 2H-benzo[c]azepine-1,3-diones (14), resulting from the insertion of a molecule of CO into the PdC bond followed by a CN reductive coupling. In contrast, the reactions of 11b or 12b with CO in the presence of residual water or 2 equiv of ROH (R = Me, Et) lead to 2-methyl-3-phenylisoindolin-1-one derivatives (15), resulting from a CO insertion followed by an intramolecular aza-Michael addition of the NHMe moiety to the activated vinyl group and subsequent hydrolysis or alcoholysis of the acylPd bond. The neutral complex [Pd('2C,O-C14H13O5)(tmeda)] (18) was synthesized by reacting the cationic derivative 10b with NaOMe in MeOH. Depalladation of 18 gives (E)-4-[methoxy(methoxycarbonyl)methylene]-2-methylisoquinoline-1,3(2H,4H)-dione (19).

  DOI：

  10.1021/om4006406