247579-49-3

Upstream product

• 121089-92-7 1-(2-bromo-4,5-dimethoxybenzyl)-3,4-dihydro-6,7-dimethoxyisoquinoline 
• 7477-50-1 2-bromo-1-chloromethyl-3,4-dimethoxy-benzene 
• 155826-73-6 N-[2-[1-(3,4-dimethoxyphenyl)]ethyl]-2-bromo-3,4-dimethoxyphenylacetamide 
• 63856-83-7 2-bromo-3,4-dimethoxyphenylacetic acid 
• 104421-97-8 2-bromo-3,4-dimethoxyphenylacetyl chloride 
• 72912-38-0 (2-bromo-3,4-dimethoxyphenyl)methanol 
• 72912-39-1 (2-bromo-3,4-dimethoxyphenyl)acetonitrile 
• 55171-60-3 2-bromo-3,4-dimethoxybenzylaldehyde 

Downstream Products

• 2934-97-6 (+/-)-tetrahydropalmatine 
• 50461-24-0 (+/-)-1-(3,4-dimethoxybenzyl)-2-ethoxycarbonyl-1,2,3,4-tetrahydro-6,7-dimethoxyisoquinoline 
• 155263-75-5 1-(2'-bromo-3',4'-dimethoxybenzyl)-2-ethoxycarbonyl-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinoline 

Relevant academic research and scientific papers

Phosphane-free Pd0-catalyzed cycloamination and carbonylation with Pd(OAc)2 and Cu(OAc)2 in the presence of K 2CO3: Preparation of benzocyclic amines and benzolactams

Phosphane-free Pd0-catalyzed intramolecular aromatic amination was studied. o-Halophenethylamines and 3-(o-halophenyl)propylamines were found to be transformed into indolines and quinolines in a catalytic system based on Pd(OAc)2 and Cu(OAc)2 in the presence of K 2CO3. Application of the method to substrates containing isoquinoline rings- the 1-(o-bromobenzyl)-3,4-dihydroisoquinolines 6, the 1-(o-bromobenzyl)-1,2,3,4-tetrahydroisoquinolines 7, and the 1-(o-bromophenethyl)isoquinolines 9- provided the indolo[2,1-a]isoquinoline and dibenzo[a,f]quinolizine ring systems 8 and 10. Extension of the method to β-carbolines (compounds 11, 12, and 17) produced the benz[f]indolo[2,3-a] indolizine-13-ones 15 and the benz[f]indolo[2,3-a]quinolizine 18. The benzo[f]pyrido[3,4-a]indolizine and indolo[f]pyrido[3,4-a]indolizin-12-one ring systems 27 and 31 were built in a similar manner. It was also found that under an atmosphere of CO the same catalytic system produced the corresponding benzolactams, the isoquino[2,1-a][2,7]naphthyridine 34 and the indolo[2,3-a]pyrido[g]quinolizin-8-one 36 [(±)-dihydronauclefine] in good yields. Copyright

Synthesis of phthalideisoquinoline and protoberberine alkaloids and indolo[2,1-α]isoquinolines in a divergent route involving palladium(0)- catalyzed carbonylation

6,7,3',4'-Alkoxy-substituted 1-(2'-bromobenzoyl)-3,4-dihydroisoquinoline methiodides 17 were treated with sodium borohydride in methanol or acetic acid to give erythro-1-(2'-bromo-α-hydroxybenzyl)-2-methyl-1,2,3,4- tetrahydroisoquinolines 19. Treatment of 17 with lithium aluminum hydride in tetrahydrofuran gave the threo-isomer 20 in preference to the erythro 19. On the basis of studies on palladium(0)-catalyzed carbonylation of 2-bromo-3,4- dimethoxybenzyl alcohol to 6,7-dimethoxyphthalide, amino alcohol 19 or 20 was treated with a catalytic amount of palladium(II) acetate and triphenylphosphine in an atmosphere of carbon monoxide in the presence of chlorotrimethylsilane and potassium carbonate in boiling toluene to give the corresponding erythro- or threo-types of phthalideisoquinoline alkaloids 1 or 2, respectively. One-pot cyclization of the erythro-amino alcohols 19 was achieved by heating in N,N-dimethylformamide containing potassium carbonate to give 2,3,8,9- or 2,3,9,10-alkoxy-substituted 5,6-dihydroindolo[2,1- α]isoquinolines 3, which have a unique tetracyclic skeleton characteristic of dibenzopyrrocoline alkaloids. Similarly, palladium-(0)-catalyzed carbonylation of 1-(2'-bromobenzyl)tetrahydroisoquinolines 21 in the presence of excess potassium carbonate was found to give 8-oxoberbines 22, which on reduction with lithium aluminum hydride can be converted to protoberberine alkaloids 4.