109802-62-2

Upstream product

• 2216-94-6 phenylpropynoic acid ethyl ester 
• 109802-33-7 {Pd(1-(dimethylamino)naphthyl-8)(MeCN)2}BF₄ 
• 108-90-7 chlorobenzene 
• 133071-22-4 [1-(dimethylamino)-8-naphthyl]lithium 
• 52753-60-3 8-iodo-1-(dimethylamino)naphthalene 

Relevant academic research and scientific papers

Palladium-catalysed synthesis of dibenzo[de,g]quinolines. A novel approach to the B-ring system of aporphine-related heterocycles

Dibenzo[de,g]quinolines 5 were formed by the palladium-catalysed heteroannulation of disubstituted alkynes and 1-iodo-10- (dimethylamino)phenanthrene (3c). Symmetric alkynes led to high levels of regioselectivity. These reactions constitute a new synthesis of the B-ring system of aporphine heterocycles.

Synthesis of N-Methylbenzoquinolines

The reaction between internal alkynes and 1-iodo-8-dimethylaminonaphthalene in the presence of catalytic amounts of a cyclopalladated compound provides a new route to N-methylbenzoquinolines.

Controlled synthesis of heterocyclic compounds through ring enlargement by alkyne insertions into the Pd-C bonds of cyclopalladated amines followed by subsequent ring closure

The chloride-bridged dimer [{Pd(dmba)(μ-Cl)}2] (1) (dmba = C6H4CH2NMe2, 2-((dimethylamino)-methyl)phenyl) reacted with 1 equiv per Pd atom of disubstituted alkynes (R1C≡CR2 in which R1 and/or R2 = CO2R, where R = Me or Et) to afford regiospecifically [{Pd(C(R2)=C(R1)C6H4CH 2NMe2)(μ-Cl)}2] (4a-c) through insertion of the alkyne into the Pd-C bond of 1. Compounds 4a-c underwent a further ring expansion by insertion of a second alkyne to give the monomers [Pd{C(R4)=C(R3)C(R2)=C-(R1)C 6H4CH2NMe2}Cl] (6a-j). The compound [Pd{C(Ph)=C(Ph)C(Ph)=C(Ph)(8-mq)}Cl] (7) (8-mq = CH2C9H6N, 8-quinolylmethyl) rearranged in boiling chlorobenzene to afford [Pd{C(Ph)=C(Ph)CH-(Ph)C(Ph)=CHC9H6N}Cl] (8), via a 1,3-hydrogen shift of the CH2 group on the adjacent olefinic bond, together with trace amounts of [{C(Ph)C(Ph)=C(Ph)C(Ph)CH2C9H6N} 2]Pd2Cl6 (9α), which has been fully characterized by an X-ray diffraction study. It shows that the organic moiety of this salt is a cationic heterocycle in which C-C and C-N bonds have been formed by a depalladation process, affording a substituted cyclobutene adduct of 1H-benzo[ij]quinolizinium. Using [{Pd(8-mq)(μ-I)}2] (2*) as well as [Pd(8-mq)(MeCN)2]BF4 (2**) as starting materials afforded good to excellent yields of cationic heterocycles 9β and 9γ having Pd2I62- and BF4- as the counteranions, respectively. Extending these easily available ligand changes to other cyclopalladated starting materials, i.e., by substitution of chloride for iodide or with cationic derivatives, led efficiently to the synthesis of several heterocyclic products. Thus [Pd-(dmba)(MeCN)2]BF4 (1**) with diphenylacetylene afforded a quantitative yield of the product [C(Ph)-=C(Ph)C(Ph)=C(Ph)C6H4CH2NMe 2]BF4 (13) whereas 1** and 2** with ethyl 3-phenylpropiolate gave the analogous heterocycles 14 and 15, respectively, as zwitterionic species. The complex [Pd(dmna)-(MeCN)2]BF4 (3**) (dmna = C10H6NMe2, 1-(dimethylamino)naphthyl-8) reacted with alkynes of the type R1C≡CR2 to afford cationic benzo[de]quinolizinium [C(R2)=C(R1)C10H6NMe 2]BF4 (17a, R1 = R2 = Ph; 17b, R1 = CO2Et, R2 = Ph). This reaction, when starting from [{Pd(dmna)(μ-I)}2] (3*), led to good yields of neutral benzo[de]quinolines 10a-d via a partial demethylation of the NMe2 group. The thermal decomposition of the monoinserted compound [{Pd(C(Ph)=C(CO2Et)C6H4CH2NMe 2)(μ-I)}2] (4a*) led to the heterocyclic products [{C(Ph)=C(CO2Et)C6H4CH=NMe}2]Pd 2I6 (11) and [C(Ph)=C-(CO2Et)C6H4CH=N] (12). The molecular structure of compound 11 has been ascertained by means of X-ray diffraction.