Intramolecular carbon-carbon vs. carbon-nitrogen bond formation in an organopalladium compound

Beydoun, N.; Pfeffer, Michel; DeCian, André; Fischer, Jean

doi:10.1021/om00056a047

Cited by 36 publications

(26 citation statements)

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“…When A is reacted with MeO 2 CC⋮CCO 2 Me, no decomposition to metallic palladium is observed and the complex [Pd(κ 2 -CCR N )(μ-Cl)] 2 ( 6 ) (Scheme ), resulting from the insertion of an alkyne molecule into the carbon−palladium bond, is isolated. Monoinserted cyclopalladated compounds of this type are well documented, ,− although very few examples are known with oxygen as the heteroatom bonded to palladium. , Complex 6 is isolated even when an excess of alkyne is used. This is the normal behavior with alkynes substituted with electron-withdrawing substituents such as CF 3 or CO 2 R. With other alkynes, the insertion of the first alkyne molecule is usually the rate-determining step and, therefore, in most cases, only the di-inserted compound is obtained …”

Section: Resultsmentioning

confidence: 99%

“…The use of organopalladium complexes in organic syntheses constitutes a topic of current interest; in particular, reactions involving arylpalladium complexes and alkynes have proved to be useful for the synthesis of various types of organic compounds. − In this paper, we report a new example of this type of reaction that gives a highly functionalized spirocyclic compound. However, although reactions of isocyanides with alkyl-, − alkynyl-, − aryl-, ,− and other 23,24 organopalladium derivatives are known to give insertion products, only a few such reactions lead directly 11,12,19-21 or after reaction with other reagents 13,18 to organic products.…”

Section: Introductionmentioning

confidence: 99%

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Palladium-Assisted Formation of Carbon−Carbon Bonds. 7.¹ Reactions of (2,3,4-Trimethoxy-6-X-phenyl)palladium Complexes with Alkynes (X = C(O)NHBu^t) and Isocyanides (X = C(O)NHBu^t, C(O)Me, CHO): Crystal and Molecular Structures of [Pd{C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4}(bpy)](CF₃SO₃), [Pd{C(CO₂Me)C(CO₂Me)C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4)}- Cl(PPh₃)], [Pd{C(NXy)C<

et al. 1997

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The mercuriation of 3,4,5-trimethoxy(N-tert-butylcarbamoyl)benzene with mercury(II) acetate and subsequent reaction with KCl leads to the formation of [Hg{C 6 The reaction of 2 with [PdCl 2 (MeCN) 2 ] and 2,2′-bipyridine (bpy) affords [Pd(C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4)Cl(bpy)] (3), which reacts with Tl(CF 3 SO 3 ) giving [Pd-{C 6 H{C(O)NHBu t }}(bpy)](CF 3 SO 3 ) (4). Complex 2 reacts with [PdCl 2 (MeCN) 2 ] and acetylenes RCtCR to give metallic palladium and the spirocyclic compound 10-(N-tert-butylcarbamoyl)-6,7-dimethoxy-1,2,3,4-tetraphenylspiro[4.5]-1,3,6,9-decatetraen-8-one (5) when R ) Ph or the monoinserted palladium complex [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}(µ-Cl)] 2 (6) when R ) CO 2 Me. By reaction of 6 with L (1:2) or PPh 3 and Tl(CF 3 SO 3 ) (1:4:2), the complexes [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}Cl(L)] (L ) PPh 3 (7), CNXy (8) (Xy ) 2,6-dimethylphenyl)) or [Pd{C(CO 2 Me)dC(CO 2 Me)C 6 H{C(O)-NHBu t }-6-(OMe) 3 -2,3,4}(PPh 3 ) 2 ](CF 3 SO 3 ) (9) are obtained respectively. The reactions of 4 and of the related complexes [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(bpy)](CF 3 SO 3 ) (10) or [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(NCMe)(bpy)](CF 3 SO 3 ) (11) with CNXy have also been studied, the following compounds being isolated: [Pd{C(dNXy)C 6 H{C(O)NHBu t }-6-(OMe) 3 -2,3,4}-(bpy)](CF 3 SO 3 ) (12) [Pd{C 6 H{C(O)Me}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (13), [Pd-{C 6 H{C(O)H}-6-(OMe) 3 -2,3,4}(CNXy)(bpy)](CF 3 SO 3 ) (14), and the ketenimine 2-(2,6dimethylphenyl)-1-(((2,6-dimethylphenyl)imino)methylene)-5,6,7-trimethoxy-3-oxoisoindoline (15). The structures of 4, 7, 12, and 15 have been determined by X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Palladium-Assisted Formation of Carbon−Carbon Bonds. 7.¹ Reactions of (2,3,4-Trimethoxy-6-X-phenyl)palladium Complexes with Alkynes (X = C(O)NHBu^t) and Isocyanides (X = C(O)NHBu^t, C(O)Me, CHO): Crystal and Molecular Structures of [Pd{C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4}(bpy)](CF₃SO₃), [Pd{C(CO₂Me)C(CO₂Me)C₆H{C(O)NHBu^t}-6-(OMe)₃-2,3,4)}- Cl(PPh₃)], [Pd{C(NXy)C<

et al. 1997

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“…The insertion reactions of alkynes into the palladium−carbon bond are interesting processes that have been used, after depalladation, − to prepare spirocyclic compounds, , indenols, indenones, carbocycles, ,,,,,, and oxygen, ,, sulfur, ,, and nitrogen heterocycles. ,,,,,− In some cases, the palladation reaction and the insertion of the alkyne form part of a catalytic cycle yielding interesting organic compounds. ,− Recently, Negishi has reported the reaction of 4-octyne with PhI and CO (10−40 atm) in the presence of Et 3 N and catalytic amounts of [PdCl 2 (PPh 3 ) 2 ] at 100−140 °C to give 2-butenolides . These compounds are formed through a sequential insertion of carbon monoxide−alkyne−carbon monoxide.…”

Section: Introductionmentioning

confidence: 99%

Palladium-Assisted Formation of Carbon−Carbon Bonds. 8.¹ Synthesis and Reactivity toward Internal Alkynes, Carbon Monoxide, and Isocyanides of Orthopalladated Dibenzylamine Complexes

et al. 1999

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By refluxing of dibenzylamine and [Pd(OAc)2]3 (3.2:1) in acetone, the orthometalated complex [Pd{C6H4(CH2NHCH2Ph)-2}(μ-OAc)]2 (1) is obtained. Metathetical reaction of 1 with NaBr affords the corresponding bromo-bridging dimer [Pd{C6H4(CH2NHCH2Ph)-2}(μ-Br)]2 (2). Neutral ligands split the bromo bridge to give monomeric complexes [Pd{C6H4(CH2NHCH2Ph)-2}Br(L)] [L = PPh3, (3a), NH(CH2Ph)2 (3b)]. Complexes [Pd{C6H4(CH2NHCH2Ph)-2}(acac)] (4) or [Pd{C6H4(CH2NHCH2Ph)-2}L2]ClO4 [L = py (5a), L2 = 1,5-cyclooctadiene (5b)] can be obtained by reacting complex 2 with [Tl(acac)] or with AgClO4 and the free ligand. Complex 2 reacts with RC⋮CR (R = Me, Et, Ph) to give [Pd{C(R)C(R)C(R)C(R)C6H4(CH2NHCH2Ph)-2}Br] [R = Me (6a), Et (6b), Ph (6c)] through a double insertion of the alkyne into the Pd−C bond. Complex 6a reacts with Tl(OTf) (OTf = CF3SO3) and neutral ligands to give [Pd{C(R)C(R)C(R)C(R)C6H4(CH2NHCH2Ph)-2}L]OTf [R = Me, L = py (7), phen (8)]. Complexes 6 insert CO or isocyanides R‘NC into the C−Pd bond to give 10-membered palladacycles [Pd{C(R)C(R)C(R)C(R)C(E)C6H4(CH2NHCH2Ph)-2}Br] [E = O, R = Me (9a), Et (9b), Ph (9c); E = NR‘, R‘ = tBu, R = Me (10a), Et (10b); R‘ = C6H3Me2-2,6, R = Me (11a), Et (11b)]. Complex 9a reacts with Tl(OTf) and neutral ligands to give [Pd{C(O)C(R)C(R)C(R)C(R)C6H4(CH2NHCH2Ph)-2}L]OTf [R = Me, L = py (12), tBuNC (13), phen (14)]. The crystal structures of 2·CH2Cl2, 7, 9a, and 13 have been solved.

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“…In the N-dimethylbenzylamine or N-dimethylferrocenylamie halo-bridged cyclo-metalation products, di-insertions proceed as shown in Eqs. and [52,[68][69][70][71][72].…”

Section: Alknylationsmentioning

confidence: 99%

“…and [52,68,[70][71][72][73][74][75][76]. The latter reactions are applied to the syntheses of the N-methylbenzo[d,e]quinolines [70,72,75].…”

Section: ð24-2þmentioning

confidence: 99%

Three types of reactions with intramolecular five-membered ring compounds in organic synthesis

Omae

2007

Journal of Organometallic Chemistry

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Intramolecular carbon-carbon vs. carbon-nitrogen bond formation in an organopalladium compound

Cited by 36 publications

References 4 publications

Palladium-Assisted Formation of Carbon−Carbon Bonds. 8.¹ Synthesis and Reactivity toward Internal Alkynes, Carbon Monoxide, and Isocyanides of Orthopalladated Dibenzylamine Complexes

Three types of reactions with intramolecular five-membered ring compounds in organic synthesis

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Intramolecular carbon-carbon vs. carbon-nitrogen bond formation in an organopalladium compound

Cited by 36 publications

References 4 publications

Palladium-Assisted Formation of Carbon−Carbon Bonds. 8.1 Synthesis and Reactivity toward Internal Alkynes, Carbon Monoxide, and Isocyanides of Orthopalladated Dibenzylamine Complexes

Three types of reactions with intramolecular five-membered ring compounds in organic synthesis

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Palladium-Assisted Formation of Carbon−Carbon Bonds. 8.¹ Synthesis and Reactivity toward Internal Alkynes, Carbon Monoxide, and Isocyanides of Orthopalladated Dibenzylamine Complexes