Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium

Seligson, Allen L.; Cowan, Robert L.; Trogler, William C.

doi:10.1021/ic00018a003

Cited by 109 publications

(51 citation statements)

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“…The successful intra-and intermolecular hydroamination of alkenes and alkynes using various catalysts such as alkali metals, [10] transition metals, [6,9,12] as well as fblock elements [8,11] reveals the feasibility of different catalytic routes for the synthesis of a variety of important amino compounds. However, a closer look to the known hydroamination reactions discloses significant problems of these catalytic methods on a large scale.…”

Section: Is This Reaction Of Potential Use Formentioning

confidence: 99%

“…[4] Active research work in this field for the past years shows possibilities of a few catalytic routes for this transformation. [5] For instance, the amine can be activated by oxidative addition to a transition metal, [6] which allows insertion of the alkene into the M À N or M À H bond, thereby promoting the hydroamination catalytically (Scheme 2). [7] Actinides [8] and early transition metal complexes [9] can activate the amine by converting it into the coordinated imide M NR and enable the reaction of C À C multiple bonds with the M À N bond (Scheme 3).…”

Section: Introduction: Hydroamination Of Olefins ± the Chemistrymentioning

confidence: 99%

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Base-Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Seayad

Tillack

Hartung

et al. 2002

Advanced Synthesis & Catalysis

393

148

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The base‐catalyzed hydroamination of olefins offers a simple and elegant access to various primary, secondary, and tertiary amines. Particular focus is placed on developments in the area of hydroamination of non‐activated olefins. Advantages and disadvantages of the methodology compared to other synthetic methods are presented. Special attention is paid to potential industrial applications of this chemistry.

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Section: Is This Reaction Of Potential Use Formentioning

confidence: 99%

Section: Introduction: Hydroamination Of Olefins ± the Chemistrymentioning

confidence: 99%

Base-Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Seayad

Tillack

Hartung

et al. 2002

Advanced Synthesis & Catalysis

393

148

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“…The reaction of Pd(OAc) 2 , dppb and H 2 led probably to the palladium dihydride intermediate [(P-P)PdH 2 ] (I) with dppb bidentate to the palladium center (step I). It was mentioned previously that the addition of acetylene to [(Cy 3 P) 2 Pd(H)(HNPh)] yielded the hydrido alkynyl complex, [(Cy 3 P)Pd(H)(CCH)] and aniline, 30 which indicates that the coordination of aniline was unlikely to take place in the reaction under the conditions of system A or B. It is most probable that the coordination of the alkyne (R-CCH) to the palladium center of complex I takes place first to give two possible intermediates, II and III.…”

Section: Proposed Mechanismmentioning

confidence: 99%

Catalytic and regioselective synthesis of gem‐ or trans‐α,β‐unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

Ali¹,

Tijani²

2003

Applied Organom Chemis

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The reaction of carbonylative addition of alkyl alkynes to aniline derivatives has been successfully achieved by a catalytic system formed of Pd(OAc) 2 and a suitable bidentate phosphine ligand. The reaction led mainly to gem-α,β-unsaturated amides (3) with Pd(OAc) 2 /1,3-bis(diphenylphosphino)propane/p-toluenesulfonic acid/CO as the catalytic system. However, the reaction catalyzed by Pd(OAc) 2 /1,4-bis(diphenylphosphino)butane/H 2 /CO in CH 2 Cl 2 as a solvent affords trans-α,β-unsaturated amides (4) as the major product. Copyright  2003 John Wiley & Sons, Ltd.KEYWORDS: carbonylative addition; alkynes; aniline; palladium; dppb; syngas; unsaturated amides INTRODUCTIONThe synthesis of saturated and unsaturated amides is an important area of organic chemistry at the industrial and academic levels. 1 In the last decade, the production of various carbonyl compounds catalyzed by various transition-metal complexes has represented an important and new route in fine chemistry. 2,3 Previously, the synthesis of N-aryl acrylamides was achieved by the reaction of aromatic amines with 2-substituted acryloyl chlorides or substituted acrylic acid. 4 The 2-substituted acrylamides are important intermediates for the synthesis of polymers.5 The direct synthesis of 2-substituted acrylamides from alkynes and amines has previously been reported using various transition-metal complexes. 6 -11 Active soluble palladium complexes are among the most widely used in selective carbonylation chemistry. For example, branched and linear α,β-unsaturated acids and their derivatives are produced by the palladiumcatalyzed carbonylation of alkynes. 12 The regioselectivity depends strongly on the catalytic system and the reaction conditions.12 Branched α,β-unsaturated acids or esters are 23 Only a few reports on palladium complexes as catalysts that can selectively lead to linear unsaturated acid derivatives as the major products have been reported.24,25 Recently, we have described a new and efficient method for the selective production of gem-or trans-α,β-unsaturated amides, esters and thiols. 26 -28 In this paper we report the results of the carbonylative addition of aniline derivatives to various alkyl alkynes producing various new and substituted gem-and trans-α,β-unsaturated amides. The reaction conditions and the catalyst system have a great effect in the inversion of the regioselectivity of the reaction. EXPERIMENTAL GeneralAniline derivatives, alkynes, palladium complexes, phosphine ligands, and carboxylic acids are commercially available materials and were used without any further purification. Materials, Nanoscience and CatalysisDry and freshly distilled solvents have been used in all experiments.1 H NMR and 13 C NMR spectra were recorded on a 500 MHz Joel l500 NMR machine. IR spectra were recorded on a Perkin Elmer 16F PC FT-TR spectrometer and are reported in wavenumbers (cm −1 ). Gas chromatography (GC) analyses were realized on HP 6890 plus chromatography. General procedure for the carbonylative coupling of terminal alkyl alky...

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“…6.6). The complex 6c was obtained as the phenol-solvated complex whose structure was determined by X-ray analysis [9]. An analogous platinum complex trans-[PtH(OPh)(PEt 3 ) 2 ] (7) was prepared by the reaction of trans-[PtH(NO 3 )(PEt 3 ) 2 ] with NaOPh (Eq.…”

Section: Preparation Of Hydrido(hydroxo) Hydrido(alkoxo) and Hydridmentioning

confidence: 99%

O–H Activation and Addition to Unsaturated Systems

Tani

Kataoka

2001

Catalytic Heterofunctionalization

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Alkyl and hydrido phenoxo complexes of nickel(II), palladium(II), and platinum(II). Hydrido amido complexes of palladium

Cited by 109 publications

References 10 publications

Base-Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Base-Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Catalytic and regioselective synthesis of gem‐ or trans‐α,β‐unsaturated amides by carbonylation of alkyl alkynes with aniline derivatives by palladium(II) and phosphine

O–H Activation and Addition to Unsaturated Systems

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