Reactions of palladium amide complexes with dimethyl acetylenedicarboxylate. Palladium-mediated carbon-nitrogen bond formation

Villanueva, Lawrence A.; Abboud, Khalil A.; Boncella, James M.

doi:10.1021/om00045a004

Cited by 53 publications

(16 citation statements)

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“…The aminopalladium complex F is then generated from intermediate E by coordination of the amine. An equilibrium between F and the amidopalladium complex G forms, followed by the coordination of alkynes and subsequent insertion gives the vinylpalladium intermediate H 14. Protonolysis of H yields the enamine 3′ and reproduces the palladium catalyst.…”

Section: Resultsmentioning

confidence: 96%

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

2004

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Section: Resultsmentioning

confidence: 96%

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

2004

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“…Such a mechanism is attractive for the following reasons. First, the formation of metallacyclobutene by nucleophilic addition, insertion into the coordinated allene, and the addition of anilide ligand to olefin are all documented. − Second, the relatively low basicity of water, alcohol, or aniline may facilitate the hydrogen transfer. With regard to ammonia, amide, and amine, their higher basicity perhaps hinders the N−H activation and thus retards the addition.…”

Section: Resultsmentioning

confidence: 99%

Coordination of Aniline to an (η¹-Allenyl)iridium Complex Leading to Hydroanilination

Chen

Chu

et al. 1997

Organometallics

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Formation of the N-arylated η 3 -aza-TMM complexes of iridium from regioselective hydroanilination of an octahedral (η 1 -allenyl)iridium complex has been studied. (OC-6-42)-In contrast, the reactions of 2 with XC 6 H 4 NH 2 (X ) F, NO 2 , MeO, H, Me), Ph 2 NH, and Ph(Me)NH result in regioselective addition at the allenyl ligand, thereby generating the N-arylated η 3 -aza-TMM complexes 5a-g. The mechanistic studies confirm that the hydroanilination is preceded by the formation of an aniline-ligated intermediate. † Based on the M.S. thesis of Y.-K.C.,

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“…Although the propensity of these intermediates to undergo CN bond‐forming reductive elimination has been well established,1 small molecule (alkene) insertion reactions of these complexes have been largely unexplored and have not been exploited in catalytic processes 2. In fact, only a single example of the stoichiometric insertion of an activated alkyne into an isolated [Pd(Ar)(NR 2 )] complex has been reported,2b and insertions of alkenes have not been demonstrated. Herein we describe a new, stereoselective, palladium‐catalyzed synthesis of pyrrolidines from γ‐( N ‐arylamino) alkenes and aryl bromides, and present mechanistic evidence that suggests the transformation proceeds by a chemoselective intramolecular insertion of an unactivated alkene into the PdN bond of an intermediate [Pd(Ar)(NRR′)] complex 3.…”

Section: Palladium‐catalyzed Synthesis Of Pyrrolidines[a]mentioning

confidence: 99%

Palladium‐Catalyzed Synthesis of N‐Aryl Pyrrolidines from γ‐(N‐Arylamino) Alkenes: Evidence for Chemoselective Alkene Insertion into PdN Bonds

2004

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In recent years, palladium(aryl)(amido) complexes have been shown to serve as key intermediates in the synthesis of aniline derivatives.[1] Although the propensity of these intermediates to undergo CÀN bond-forming reductive elimination has been well established, [1] small molecule (alkene) insertion reactions of these complexes have been largely unexplored and have not been exploited in catalytic processes. [2] In fact, only a single example of the stoichiometric insertion of an activated alkyne into an isolated [Pd(Ar)(NR 2 )] complex has been reported, [2b] and insertions of alkenes have not been demonstrated. Herein we describe a new, stereoselective, palladium-catalyzed synthesis of pyrrolidines from g-(Narylamino) alkenes and aryl bromides, and present mechanistic evidence that suggests the transformation proceeds by a chemoselective intramolecular insertion of an unactivated alkene into the PdÀN bond of an intermediate [Pd(Ar)(NRR')] complex.[3] This reaction allows convergent access to substituted pyrrolidines, which are found in a variety of natural products.[4] In contrast to most methods available for the synthesis of substituted pyrrolidines, [5] this reaction effects intramolecular CÀN bond formation with concomitant intermolecular formation of a C1'ÀC bond. [6] In preliminary studies we employed g-aminoalkene substrates with N-aryl substituents because of their ease of preparation and handling. After optimization of the reaction conditions we found that the reaction of N-phenyl-4-pentenylamine (1 a) with 2-bromonaphthalene in the presence of NaOtBu and a catalytic amount of [Pd 2 (dba) 3 ]/dppb (1 mol %; dppb = 1,4-bis(diphenylphosphanyl)butane) at 60 8C in toluene afforded the desired N-aryl 2-(b-naphthylmethyl)pyrrolidine 2 a and regioisomeric product 3 a in 94 % yield and a 25:1 ratio [Eq. (1)].As shown in Table 1, the reactions of electron-rich, electron-neutral, and electron-deficient N-aryl amine derivatives with a variety of aryl bromide coupling partners proceeded in good yield. A number of functional groups are

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Reactions of palladium amide complexes with dimethyl acetylenedicarboxylate. Palladium-mediated carbon-nitrogen bond formation

Cited by 53 publications

References 0 publications

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

Coordination of Aniline to an (η¹-Allenyl)iridium Complex Leading to Hydroanilination

Palladium‐Catalyzed Synthesis of N‐Aryl Pyrrolidines from γ‐(N‐Arylamino) Alkenes: Evidence for Chemoselective Alkene Insertion into PdN Bonds

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Reactions of palladium amide complexes with dimethyl acetylenedicarboxylate. Palladium-mediated carbon-nitrogen bond formation

Cited by 53 publications

References 0 publications

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

Aquapalladium Complex: A Stable and Convenient Catalyst for the Intermolecular Hydroamination of Alkynes

Coordination of Aniline to an (η1-Allenyl)iridium Complex Leading to Hydroanilination

Palladium‐Catalyzed Synthesis of N‐Aryl Pyrrolidines from γ‐(N‐Arylamino) Alkenes: Evidence for Chemoselective Alkene Insertion into PdN Bonds

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Coordination of Aniline to an (η¹-Allenyl)iridium Complex Leading to Hydroanilination