74035-73-7

Upstream product

• 95427-40-0 1-(3-hydroxy-4-methoxybenzyl)-6-methoxy-3,4-dihydroisoquinoline 
• 154013-12-4 (Z)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methylene>-6-methoxy-1,2,3,4-tetrahydroisoquinoline 
• 1033384-84-7 C₁₈H₁₉NO₃*H₃O₄P 
• 2039-67-0 2-(3-methoxyphenyl)-1-ethanamine 
• 74007-21-9 N-<2-(3-methoxyphenyl)ethyl>(3-hydroxy-4-methoxyphenyl)acetamide 
• 1131-94-8 homoisovanillic acid 
• 154013-19-1 (R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline 

Downstream Products

• 154013-19-1 (R)-2-Formyl-1-<(3-hydroxy-4-methoxyphenyl)methyl>-6-methoxy-1,2,3,4-tetrahydroisoquinoline 

Relevant academic research and scientific papers

PREPARATION OF HEXAHYDROISOQUINOLINES FROM DIHYDROISOQUINOLINES

The present invention is directed to processes for the synthesis of morphinans. In particular, a process for the asymmetric reduction of an imine moiety in a 3,4-dihydroisoquinoline to produce a tetrahydroisoquinoline, followed by a Birch reduction to pro

Chemistry of opium alkaloids, 45. Improvements in the total synthesis of morphine

The chiral 1,2,3,4-tetrahydroisoquinoline intermediates in the Price and Beyerman routes to morphine, (+)-(R)-1-(3-hydroxy-4-methoxybenzyl)-6-methoxy- 1,2,3,4-tetrahydroisoquinoline (6) and (+)-(R)-1-(3,5-dibenzyloxy-4- methoxybenzyl)-6-methoxy-1,2,3,4-tetrahydroisoquinoline (5), were prepared in high ee by ruthenium-catalyzed asymmetric transfer hydrogenation of the corresponding imine precursors (Noyori method). The yield of the key raw material in the Beyerman route, 3,5-dibenzyloxy-4-methoxyphenylacetric acid (1), starting from gallic acid methyl ester (7) was improved by a factor of 5 over previously described syntheses. Key steps in the new procedure are the selective formation of methyl 3,5-dihydroxy-4-methoxybenzoate (9) via the 3,5-diacetate and an improved benzylation of the hydroxyl groups in 9.

General asymmetric synthesis of isoquinoline alkaloids. Enantioselective hydrogenation of enamides catalyzed by BINAP-ruthenium(II) complexes

In the presence of a small amount of RuX2[(R)- or (S)-BINAP] (X = anionic ligand) a wide range of (Z)-2-acyl-1-benzylidene-1,2,3,4- tetrahydroisoquinolines are hydrogenated to give the saturated products in nearly quantitative yields and in high (up to 100%) optical yields. The enamide substrates are selectively prepared by N-acylation of the corresponding 1-benzylated 3,4-dihydroisoquinolines under suitable acylation conditions; some crystalline materials having low solubility are obtained by a second-order Z/E stereomutation technique utilizing the double-bond photolability and lattice energy effects. This asymmetric hydrogenation sets the key stereogenic center in a predictable manner, either R or S flexibly, at the C(1) position of the benzylated tetrahydroisoquinolines. The chiral products are converted by standard functional group modification to tetrahydropapaverine, laudanosine, tretoquinol, norreticuline, etc. Hydrogenation of the simple 1-methylene substrate is used for synthesis of salsolidine. This enantioselective hydrogenation is applied to the synthesis of morphine and its artificial analogues such as morphinans and benzomorphans of either chirality. A mnemonic device is presented for predicting the reactivity and enantiofacial selection of the BINAP-Ru catalyzed hydrogenation. Reaction with BINAP-Rh catalyst proceeds with a lower enantioselectivity and an opposite sense of asymmetric induction.