Palladium-catalyzed Amination Research Articles

Facile synthesis of soluble aromatic poly(amide amine)s via C-N coupling reaction: Characterization, thermal, and optical properties

Aromatic poly(amide amine)s (APAAs), as novel high-performance polymers, have been obtained by the condensation polymerization of N,N'-bis(4-bromobenzoyl)-p-phenylenediamine with two different primary aromatic diamines via palladium-catalyzed aryl amination reaction. The structures of the polymers are characterized by means of FTIR, 1H NMR spectroscopy, and elemental analysis, the results show a good agreement with the proposed structures. DSC and TGA measurements exhibit that polymers possess high glass transition temperature (Tg > 240 °C) and good thermal stability with high decomposition temperatures (T5 > 400 °C). These novel polymers also display good solubility. In addition, due to its special structure, APAA-2 is endowed with significantly strong photonic luminescence in N,N-dimethylformamide and good electroactivity. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4845–4852

Use of a Readily Removable Auxiliary Group for the Synthesis of Pyrrolidones by the Palladium‐Catalyzed Intramolecular Amination of Unactivated γ C(sp3)H Bonds

Easy on, easy off: Directing groups found to promote the palladium-catalyzed amination of γ C(sp(3) )H and C(sp(2) )H bonds of secondary amides included 5-methoxy-8-aminoquinoline, which can be removed under mild conditions (see scheme; CAN=ceric ammonium nitrate). In conjunction with a β-CH methylation or γ-CH arylation step, the γ-C(sp(3) )H amination provided access to complex pyrrolidones from readily available precursors.

Palladium-catalyzed synthesis of N-arylated carbazoles using anilines and cyclic diaryliodonium salts.

The direct synthesis of N-arylated carbazoles through a palladium-catalyzed amination of cyclic iodonium salts with anilines is described. In particular, electron-poor aniline derivatives reacted smoothly with only 5 mol % of Pd(OAc)2 as catalyst to give the desired products in up to 71% yield. Furthermore, the reactivity of cyclic iodonium salts is compared with the reactivity of the corresponding cyclic bromonium analogues.

Preparation of a Nylon-11 Precursor from Renewable Canola Oil

We report a multi-catalytic sequence to a valuable nylon-11 precursor, methyl 11-aminoundecanoate, which is prepared by a ruthenium-catalysed cross-metathesis and a highly regioselective palladium-catalysed amination–hydrogenation reaction, from canola oil, a renewable, natural vegetable oil feedstock.

ChemInform Abstract: Aminocarbonylation of (Hetero)aryl Bromides with Ammonia and Amines Using a Palladium/DalPhos Catalyst System.

AbstractAmmonia acts as both nucleophile and base in these reactions.

Palladium-Catalyzed Amination of Dichloroquinolines with Adamantane-Containing Amines

Pd-catalyzed amination of isomeric 2,6-, 2,8-, 4,8- and 4,7-dichloroquinolines was studied using adamantane-containing amines in which substituents at the nitrogen atom differ in bulkiness. The selectivity of the amination of 2,6-dichloroquinoline was very low, substantially better results were obtained with 2,8-dichloroquinoline, and 4,8- and 4,7-dichloroquinolines provided the best yields of the amination products. Diamination of 4,8- and 4,7-dichloroquinolines was carried out with two amines which differ strongly in the bulkiness of the alkyl group. In the majority of cases BINAP ligand was successfully applied, however, it had to be replaced with DavePhos in certain reactions when using the most sterically hindered amine as well as for the diamination reactions.

Palladium-Catalyzed Amination in the Synthesis of Macrocycles Comprising Two Naphthalene And Two Polyamine Moieties

Two approaches were elaborated for the synthesis of macrocycles comprising two naphthalene and two polyamine moieties (cyclodimers). The first one includes the synthesis of N,N’-bis(7-bromonaphth-2-yl) substituted polyamines via Pd-catalyzed amination reaction of polyamine with excess of 2,7-dibromonaphthalene, followed by the Pd-catalyzed macrocyclization reaction with appropriate polyamine. The second route comprises the formation of 2,7-bis(polyamine) substituted naphthalenes which are used in situ for the macrocyclization with 2,7-dibromonaphthalene. The yields of cyclodimers are dependent on the nature of polyamines and catalytic systems employed. The two synthetic routes were compared and the one-pot method was found to be advantageous providing better yields of the target products.

Arylation of adamantanamines: VI. Palladium-catalyzed arylation of amines and diamines of the adamantane series with 3-bromopyridine

Palladium-catalyzed amination of 3-bromopyridine with amines of the adamantane series in the presence of Pd(dba)2/L [L = 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl or 2-dimethylamino-2′-dicyclohexylphosphinobiphenyl] gave the desired N-(pyridin-3-yl)-substituted amines in 74–97% yields. Diamines of the adamantane series reacted with 2 equiv of 3-bromopyridine in a complicated fashion to produce mono- and triaryl-substituted derivatives as by-products, while the yields of N,N′-diarylation products were 18–56%.

Arylation of adamantanamines: V. Palladium-catalyzed amination of isomeric chloroquinolines with diamines of the adamantane series

Palladium-catalyzed arylation of diamines of the adamantane series with isomeric 2-, 4-, and 6-chloroquinoline was studied, and optimal conditions for the synthesis of the corresponding N,N′-diaryl derivatives were found. N,N-Diarylation products of primary amino groups in the diamines bearing 2-aminoethyl and 4-aminophenyl substituents were readily formed.

Catalytic Enantioselective Desymmetrisation as a Tool for the Synthesis of Hodgkinsine and Hodgkinsine B

Two palladium-catalysed amination protocols are deployed in the desymmetrisation of the complex dimeric alkaloid meso-chimonanthine. The power of these transformations is showcased in an efficient formal and total synthesis of the natural products hodgkinsine and hodgkinsine B, respectively.

Double Palladium-Catalyzed Synthesis of Azepines

The synthesis of new 5H-pyridobenzazepine and 5H-dipyridoazepine compounds using as key step a palladium-catalyzed amination–cyclization reaction is reported. By choosing an appropriate combination of ligands and reactants under standardized reaction conditions, N- and S-tricyclic products can be prepared in one step from the appropriate stilbenes.

Meso-substituted Porphyrin Derivatives via Palladium-Catalyzed Amination Showing Wide Range Visible Absorption: Synthesis and Photophysical Studies

In recent years, there has been a growing interest in the design and synthesis of chromophores, which absorb in a wide region of the visible spectrum, as these constitute promising candidates for use as sensitizers in various solar energy conversion schemes. In this work, a palladium-catalyzed coupling reaction was employed in the synthesis of molecular triads in which two porphyrin or boron dipyrrin (BDP) chromophores are linked to the meso positions of a central Zn porphyrin (PZn) ring via an amino group. In the resulting conjugates, which strongly absorb over most of the visible region, the electronic properties of the constituent chromophores are largely retained while detailed emission experiments reveal the energy transfer pathways that occur in each triad.

ChemInform Abstract: Improved Protocol for Indoline Synthesis via Palladium‐Catalyzed Intramolecular C(sp2)—H Amination.

AbstractThis method can be applied to prepare the betanin precursor (VIc).

ChemInform Abstract: Palladium‐Catalyzed Amination of Chloromethylnaphthalene and Chloromethylanthracene Derivatives with Various Amines.

Palladium-catalyzed amination of chloromethylnaphthalene and chloromethylanthracene derivatives to produce naphthylamines and anthrylamines in satisfactory to good yields has been developed. The unprecedented amination reactions proceeded smoothly under mild conditions in the presence of Pd(PPh(3))(4) as a catalyst.

Palladium-Catalyzed Intermolecular Domino Reaction of gem-Dibromo­enynes with Anilines; A One-Pot Synthesis of Quinolines and Quinolinones

An efficient domino process involving palladium-catalyzed amination of an alkenyl bromide, 1,5-H transfer, annulation via 6-exo-dig electrophilic cyclization, and palladium-catalyzed etherification, is described. This reaction provides an efficient one-pot synthesis of multi-substituted quinolines and quinolinones from gem-dibromoenynes and anilines.

Synthesis of porphyrin indolin-2-one conjugates via palladium-catalyzed amination reactions

New porphyrin indolin-2-one conjugates were synthesized via palladium-catalyzed amination reactions of iodinated and dibrominated indolin-2-one derivatives with (2-amino-5,10,15,20-tetraphenylporphyrinato)nickel(II). The combination of palladium catalysts and the phosphine ligand dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos) is an effective methodology for catalyzing the coupling of 5-iodo-, 5,7-dibromo- and 4,6-dibromo-1,3,3-trimethylindolin-2-one with 2-aminoporphyrin to give the corresponding mono-(2-aminoporphyrinyl)- and di-(2-aminoporphyrinyl)-substituted indolin-2-ones in satisfactory yields under mild conditions. The mono brominated porphyrinic derivatives also underwent cross-coupling reactions under similar catalytic conditions. The studies also demonstrated that the course of the coupling process depends on factors, such as the catalytic system, number and position of the halogen substituents and the heating condition. Insights into the reactivity trends of the 5-iodo; 4,6- and 5,7-dibrominated indolin-2-one derivatives was carried out using theoretical calculations performed using density-functional theory with the B3LYP functional.

Palladium-catalyzed amination in the synthesis of aza- and diazacrown trismacrocyclic compounds

Palladium-catalyzed C-N-cross-coupling of N,N′-bis(bromobenzyl) diazacrown compounds with two equivalents of 1-aza-15-crown-5 and 1-aza-18-crown-6 ethers furnished trismacrocyclic compounds with isolated macrocycles. Macrotricyclic cryptands were obtained when diazacrown ethers were used as N-components.

A Pentacyclic Nitrogen‐Bridged Thienyl–Phenylene–Thienyl Arene for Donor–Acceptor Copolymers: Synthesis, Characterization, and Applications in Field‐Effect Transistors and Polymer Solar Cells

A pentacyclic benzodipyrrolothiophene (BDPT) unit, in which two outer thiophene rings are covalently fastened with the central phenylene ring by nitrogen bridges, was synthesized. The two pyrrole units embedded in BDPT were constructed by using one-pot palladium-catalyzed amination. The coplanar stannylated Sn-BDPT building block was copolymerized with electron-deficient thieno[3,4-c]pyrrole-4,6-dione (TPD), benzothiadiazole (BT), and dithienyl-diketopyrrolopyrrole (DPP) acceptors by Stille polymerization. The bridging nitrogen atoms make the BDPT motif highly electron-abundant and structurally coplanar, which allows for tailoring the optical and electronic properties of the resultant polymers. Strong photoinduced charge-transfer with significant band-broadening in the solid state and relatively higher oxidation potential are characteristic of the BDPT-based polymers. Poly(benzodipyrrolothiophene-alt-benzothiadiazole) (PBDPTBT) achieved the highest field-effect hole mobility of up to 0.02 cm(2) V(-1) s(-1). The photovoltaic device using the PBDPTBT/PC(71)BM blend (1:3, w/w) exhibited a V(oc) of 0.6 V, a J(sc) of 10.34 mA cm(-2), and a FF of 50%, leading to a decent PCE of 3.08%. Encouragingly, the device incorporating poly(benzodipyrrolothiophene-alt-thienopyrrolodione) (PBDPTTPD)/PC(71)BM (1:3, w/w) composite delivered a highest PCE of 3.72%. The enhanced performance arises from the lower-lying HOMO value of PBDPTTPD to yield a higher V(oc) of 0.72 V.

Palladium-Catalyzed Amination of Chloromethylnaphthalene and Chloromethylanthracene Derivatives with Various Amines

Palladium-catalyzed amination of chloromethylnaphthalene and chloromethylanthracene derivatives to produce naphthylamines and anthrylamines in satisfactory to good yields has been developed. The unprecedented amination reactions proceeded smoothly under mild conditions in the presence of Pd(PPh(3))(4) as a catalyst.

ChemInform Abstract: Palladium‐Catalyzed Tandem N‐Vinylation and Cyclization of Anilines and Haloenynes: An Efficient Approach to Substituted Quinolines.

AbstractThe reaction can be performed successfully with bromo‐ and iodoenynes.