2013
DOI: 10.1021/om4000192
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Synthesis and Reactivity of Ortho-Palladated 3-Phenylpropanamides. Insertion of CO, XyNC, and Alkynes into the Pd–C Bond. Synthesis of Seven- and Nine-Membered Palladacycles and Benzazepine- and Benzazonine-Based Heterocycles

Abstract: Aryl palladium complexes [Pd{C 6 H 4 (CH 2 ) 2 C(O)-NRR′)-2}I(tmeda)] [NRR′ = NH 2 (1a), NHMe (1b), NMe 2 (1c); tmeda = N,N,N′,N′-tetramethylethylenediamine] are prepared by oxidative addition of the corresponding 3-(2iodophenyl)propanamides to "Pd(dba) 2 " ([Pd 2 (dba) 3 ]•dba; dba = dibenzylideneacetone) in the presence of tmeda. The cationic seven-membered palladacycles [Pd{κ 2 C,O-C 6 H 4 (CH 2 ) 2 C(O)-NRR′)-2}(tmeda)]TfO (2a−c) are obtained by reacting 1a−c with AgTfO. Neutral amidate complexes of the ty… Show more

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Cited by 28 publications
(31 citation statements)
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“…During the past few years, we have been interested in the synthesis of ortho -functionalized aryl palladium complexes with the purpose of studying their reactivity toward unsaturated molecules. Following this idea, we have reported insertion reactions of CO, RNC, acetylenes, olefins, O 2 , nitriles, cyanamides, isothiocyanates, carbodiimines, or allenes as well as sequential insertion reactions of some of these reagents into the C–Pd bond of ortho -functionalized aryl palladium complexes containing the ortho -group −CHO, −C­(O)­Me, , −CN, −(CRR′) n NH 2 ( n = 0–2), −(CRR′)­NHOH, −CH 2 OEt, −CHCHR, , C­(O)­NHBu t , OH, −NPPh 3 , −CH­(SCH 2 ) 2 , −CH­(SR) 2 , −SR, −NCNR, −NCS, −NHC­(O)­NRR′, −(CH 2 ) n C­(O)­NRR′ ( n = 1, 2), and −NHC­(Me)­CHC­(O)­Me . Interestingly, the resulting complexes were not only the expected insertion products but frequently also the result of some process that produced new types of complexes ,,,, or, after depalladation, new organic products. ,,, Related reactions have also been reported by other groups …”
Section: Introductionmentioning
confidence: 99%
“…During the past few years, we have been interested in the synthesis of ortho -functionalized aryl palladium complexes with the purpose of studying their reactivity toward unsaturated molecules. Following this idea, we have reported insertion reactions of CO, RNC, acetylenes, olefins, O 2 , nitriles, cyanamides, isothiocyanates, carbodiimines, or allenes as well as sequential insertion reactions of some of these reagents into the C–Pd bond of ortho -functionalized aryl palladium complexes containing the ortho -group −CHO, −C­(O)­Me, , −CN, −(CRR′) n NH 2 ( n = 0–2), −(CRR′)­NHOH, −CH 2 OEt, −CHCHR, , C­(O)­NHBu t , OH, −NPPh 3 , −CH­(SCH 2 ) 2 , −CH­(SR) 2 , −SR, −NCNR, −NCS, −NHC­(O)­NRR′, −(CH 2 ) n C­(O)­NRR′ ( n = 1, 2), and −NHC­(Me)­CHC­(O)­Me . Interestingly, the resulting complexes were not only the expected insertion products but frequently also the result of some process that produced new types of complexes ,,,, or, after depalladation, new organic products. ,,, Related reactions have also been reported by other groups …”
Section: Introductionmentioning
confidence: 99%
“…Unsaturated species, such as isocyanides, carbon monoxide, and alkenes, readily insert into the Pd–C bond of aryl-complexes to afford organometallic iminoacyl, acyl-, and alkyl-derivatives or organic compounds upon further decomposition. , The accepted mechanism of these insertion reactions into the Pd–C bond involves (1) coordination of the unsaturated molecule to the metal center and (2) migratory insertion of the aryl group to the coordinated ligand. , These organometallic intermediates can be stable enough to be isolated or evolve through a reductive elimination process to afford the corresponding organic derivatives. , …”
Section: Resultsmentioning
confidence: 99%
“…In this way each molecule has two donor and two acceptor interactions and is involved in two R Four structures have been reported for eight-and nine-membered cyclic NH carboximides all of which, viz. 278 [234], 279 [235], 280 [235] and 281 [236] (Figure 80) exist as simple NH to CO hydrogen-bonded R…”
Section: Bridged Six-membered Ring Imidesmentioning
confidence: 99%
“…Four structures have been reported for eight-and nine-membered cyclic NH carboximides all of which, viz. 278 [234], 279 [235], 280 [235] and 281 [236] (Figure 80) exist as simple NH to CO hydrogen-bonded R 2 2 (8) dimers of pattern A. It is notable that between the closely similar compounds 279 and 280 the opposite imide CO is involved.…”
Section: Eight-and Nine-membered Cyclic Carboximidesmentioning
confidence: 99%