Palladium-catalyzed oligomerization

Takacs JM (2002) Palladium-Catalyzed Oligomerization and Polymerization of Dienes and Related Compounds. In Negishi E, de Meijere A (eds) Handbook of Organopalladium Chemistry for Organic Synthesis. Wiley, New York, p 1579... 

IV.10.1 Palladium-Catalyzed Oligomerization and Polymerization of Dienes and Related Compounds... 

Ito Y, Kojima Y, Suginome M (1996) New synthesis of quinoxaline derivatives based on palladium catalyzed oligomerization of 1,2-diisocyanoarenes. Heterocycles 42(2) 597-615. doi 10.3987/COM-95-S51... 

Arylamines display electronic properties that are favorable for materials science. In particular, arylamines are readily oxidized to the aminium form, and this leads to conductivity in polyanilines, hole-transport properties in triarylamines, stable polyradicals with low energy or ground-state, high-spin structures, and the potential to conduct electrochemical sensing. The high yields of the palladium-catalyzed formation of di- and triarylamines has allowed for ready access to these materials as both small molecules and discrete oligomeric or polymeric macromolecules. 

Ionic liquids can be used as replacements for many volatile conventional solvents in chemical processes see Table A-14 in the Appendix. Because of their extraordinary properties, room temperature ionic liquids have already found application as solvents for many synthetic and catalytic reactions, for example nucleophilic substitution reactions [899], Diels-Alder cycloaddition reactions [900, 901], Friedel-Crafts alkylation and acylation reactions [902, 903], as well as palladium-catalyzed Heck vinylations of haloarenes [904]. They are also solvents of choice for homogeneous transition metal complex catalyzed hydrogenation, isomerization, and hydroformylation [905], as well as dimerization and oligomerization reactions of alkenes [906, 907]. The ions of liquid salts are often poorly coordinating, which prevents deactivation of the catalysts. 

Catalyzed by Palladium (See Oligomerization Polymerization by Homogeneous Catalysis)... 

Reaction of diarylamines with aryl nonaflates as part of the synthesis of discrete oligomeric triarylamines has also been reported104. Only one paper reports the palladium-catalyzed reactions of diarylamines with aryl tosylates this reaction was conducted with X-phos 31 (Figure 8) as the ligand in mixed solvents of 5 1 toluene t-butanol98. 

Pentose-Based Surfactants from Palladium-Catalyzed Butadiene Oligomerization. . 86... 

Pentose-based surfactants have also been obtained through Pd-catalyzed oligomerization of butadiene [27-29]. This aspect is developed in Palladium-catalyzed telomerization of butadiene with polyols from mono to polysaccharides devoted to this type of products. 

Simple 1,3-dienes such as 1,3-butadiene, isoprene, and related compounds undergo efficient metal-catalyzed oligomerization. Under palladium catalysis, diene dimerization is the most common oligomerization reaction observed. Four modes of dimerization have been reported (Scheme 1) (i) [2 + 2] cycloaddition to afford 1,2-divinylcyclobutane (1) (ii) [4 -I- 2] cycloaddition to afford 4-vinylcyclohexene (2) (iii) [4 + 4] cycloaddition to afford 1,4-cyclooctadiene (3) and (iv) linear dimerization to afford 1,3,7-octatriene (4). 

Carbonylation was applied in oligomerizations and polycondensations as well, even though most of the previous work focused on monocarbonylation reactions. Chaudhari and colleagues reported a palladium-catalyzed carbonylation-polycon-densation reaction of aromatic diiodides and aminohydroxy compounds [117]. With their methodology, alternating polyesteramides were prepared in chlorobenzene with l,8-diaza-bicyclo[5.4.0]undec-7-ene (DBU) as a base under 3 bar of carbon monoxide at 120 °C (Scheme 2.8). 

VL8 Synthesis of Oligomeric and Polymeric Materials via Palladium-Catalyzed Successive Migratory Insertion of Isonitriles... 

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