Toward poly(aminophthalimide), structures of dimers and trimers

Abstract

Abstract-Poly(aminophthalimide) (PAP) dimers and trimers have been synthesized by palladium-catalyzed cross-coupling reactions of 3-aminophthalimides with 3-chloro-and 3,6-dichlorophthalimide, respectively. When Pd(OAc) 2 , XPhos (2-dicyclohexylphosphino-2 0 ,4 0 ,6 0 -triisopropylbiphenyl), and K 3 PO 4 are used, the C-N bond-forming reactions proceed quantitatively. The structures of those oligomers are examined by experimental and theoretical techniques including NMR, IR, single-crystal X-ray diffraction, and DFT calculations. The strong preference for cisoid structure of the diphthalimidylamine unit bearing a bifurcate hydrogen bonding is disclosed. Therefore, the aminophthalimide backbone is a highly promising candidate for the construction of a dynamically ordered helical structure.

Biaryl Phosphane Ligands in Palladium‐Catalyzed Amination

“…[279] These authors noted that the choice of base and palladium source was essential in obtaining an optimal yield of product and that aryl chlorides gave higher yields of the desired oligomers than either aryl bromides or iodides as coupling partners.…”

Biarylphosphanliganden in der palladiumkatalysierten Aminierung

“…[279] Die Auswahl der Base und der Palladiumquelle war für eine optimale Produktausbeute wesentlich, und Kupplungen mit Arylchloriden ergaben die gewünschten Oligomere in höheren Ausbeuten als Reaktionen mit Arylbromiden oder -iodiden.…”

Ferrocenylimidazoline palladacycles: Syntheses, crystal structures and applications as catalysts for Suzuki cross coupling reaction in water

“…More recently, we have found that ferrocenylimidazoline palladacycles are competent for the catalyzed Suzuki reactions of a wide range of aryl bromides at room temperature under aerobic conditions [6]. As an extension of this study, we report herein the syntheses, characterizations and crystal structures of two representative triphenylphosphine adducts of dimeric cyclopalladated ferrocenylimidazoline complexes 2a and 2b as well as their catalytic reactivity in the Suzuki reaction of aryl chlorides with phenylboronic acid in neat water under air atmosphere.…”

“…The preparations of compounds 2a and 2b are as follows: cyclopalladated ferrocenylimidazoline chloro bridge dimer 1a [6] was treated with two equivalents of PPh 3 in methanol at room temperature for 1 h (Scheme 1). The mixture was concentrated under reduced pressure and the residue was purified by silica gel chromatogram (dichloromethane) to give orange-yellow solid 2a (yield: 88%) [7].…”

“…The intermolecular hydrogen bond between chlorine atom and the adjacent C-H group of imidazoline (C12 (7), Pd(1)-Cl(1) 2.3840 (6) and C(2)-Pd(1)-N(1) 79.59 (8), C(2)-Pd(1)-P(1) 93.60 (7), N(1)-Pd(1)-P(1) 172.67(5), C(2)-Pd(1)-Cl(1) 170.46 (7) also exist the C-HÁ Á Áp interactions (2.787 Å , 141.0°) between C(9)-H(9) in the Cp ring and the adjacent Cp ring (see Figs. 3 and 4).…”