Reactivity of Ortho-Palladated Benzamides toward CO,Isocyanides, and Alkynes. Synthesis of Functionalized Isoindolin-1-onesand 4,5-Disubstituted Benzo[c]azepine-1,3-diones.
In: Organometallics, Jg. 32 (2013-08-26), Heft 16, S. 4664-4676
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Zugriff:
Aryl palladium complexes [Pd{C6H4C(O)NRRâ²-2}I(tmeda)][NRRâ² = NH2(1a), NHMe (1b), NMe2(1c); tmeda = N,N,Nâ²,Nâ²-tetramethylethylenediamine] areprepared by oxidative addition of the corresponding 2-iodophenylbenzamidesto âPd(dba)2â ([Pd2(dba)3]·dba; dba = dibenzylideneacetone) in the presence of tmeda.Cationic cyclometalated derivatives [Pd{κ2C,O-C6H4C(O)NRRâ²-2}(tmeda)]TfO(2aâc) are obtained by iodide abstractionfrom the appropriate complex 1with AgTfO, while thedeprotonation of the amide function of 1aor 1bwith KOtBu gives the neutral amidatecomplexes [Pd{κ2C,N-C6H4C(O)NR-2}(tmeda)] [R = H (3a), Me(3b)]. Complexes 2a,band 3a,breact with CO under mild conditions to yieldphthalimide (4a) or N-methylphthalimide(4b), whereas the reactions of derivatives 1cand 2cwith CO are very slow and give N1,N1,N2,N2-tetramethylphthalamide andphthalic anhydride. The reaction of 1bwith 1 equiv ofXyNC (Xy = 2,6-dimethylphenyl) or tBuNCaffords Pd(0), (tmedaH)I, and 3-(2,6-dimethylphenylimino)-2-methylisoindolin-1-one(5b) or 3-(tert-butylimino)-2-methylisoindolin-1-one(5bâ²), respectively, while complex 1creacts with 3 equiv of XyNC to give trans-[Pd{C(î»NXy)C6H4C(O)NMe2-2}I(CNXy)2] (6). The seven-membered palladacycles [Pd{κ2C,O-C(X)î»C(Xâ²)C6H4C(O)NRRâ²-2}(tmeda)]TfO [NRRâ² = NH2and X = Ph, Xâ² = Me (7a); NRRâ² = NHMeand X = Ph, Xâ² = Me (7b), X = Xâ² = Ph (8b), Et (9b), CO2Me (10b), X = CO2Me, Xâ² = Ph (11b), X = CO2Et, Xâ² = Ph (12b); NRRâ² = NMe2and X = Xâ² = Ph (8c), Et (9c)] are obtained from the reactions of 2aâcwith alkynes. Treatment of complexes 7a, 7b, 8b, and 9bwith CO at room temperaturegives the corresponding 2H-benzo[c]azepine-1,3-diones (14), resulting from the insertionof a molecule of CO into the PdâC bond followed by a CâNreductive coupling. In contrast, the reactions of 11bor 12bwith CO in the presence of residual water or2 equiv of ROH (R = Me, Et) lead to 2-methyl-3-phenylisoindolin-1-onederivatives (15), resulting from a CO insertion followedby an intramolecular aza-Michael addition of the NHMe moiety to theactivated vinyl group and subsequent hydrolysis or alcoholysis ofthe acylâPd bond. The neutral complex [Pd(κ2C,O-C14H13O5)(tmeda)](18) was synthesized by reacting the cationic derivative 10bwith NaOMe in MeOH. Depalladation of 18gives(E)-4-[methoxy(methoxycarbonyl)methylene]-2-methylisoquinoline-1,3(2H,4H)-dione (19). [ABSTRACT FROM AUTHOR]
Titel: |
Reactivity of Ortho-Palladated Benzamides toward CO,Isocyanides, and Alkynes. Synthesis of Functionalized Isoindolin-1-onesand 4,5-Disubstituted Benzo[c]azepine-1,3-diones.
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Autor/in / Beteiligte Person: | Frutos-PedrenÌo, Roberto ; GonzaÌlez-Herrero, Pablo ; Vicente, JoseÌ ; Jones, Peter G. |
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Zeitschrift: | Organometallics, Jg. 32 (2013-08-26), Heft 16, S. 4664-4676 |
Veröffentlichung: | 2013 |
Medientyp: | academicJournal |
ISSN: | 0276-7333 (print) |
DOI: | 10.1021/om4006406 |
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