3-Carbolines reaction with benzaldehyde

For the kinetically controlled formation of 1,3-disubstituted tetrahydro-P-carbolines, placing both substituents in equatorial positions to reduce 1,3-diaxial interactions resulted in the cw-selectivity usually observed in these reactions." Condensation reactions carried out at or below room temperature in the presence of an acid catalyst gave the kinetic product distribution with the cw-diastereomer being the major product observed, as illustrated by the condensation of L-tryptophan methyl ester 41 with benzaldehyde. At higher reaction temperatures, the condensation reaction was reversible and a thermodynamic product distribution was observed. Cis and trans diastereomers were often obtained in nearly equal amounts suggesting that they have similar energies."... 

The Eschweiler reaction (formaldehyde and formic acid) has been used for the pyr-A-methylation of l-methyl-l,2,3,4-tetrahydro-j8-carboline, as has formaldehyde and hydrogen in the presence of Raney nickel. Tetrahydroharmine has been reported to react with benzaldehyde to yield a condensation product, C33H36N403, which is presumably a pyr-iV-substituted derivative (318). It is not known whether a similar condensation product of benzaldehyde with harm-aline is a C- or V-substituted derivative of harmaline. Conden-... 

The reaction of 148 with 10% HCl-MeOH afforded selective hydrolysis of the amide to form the 3-aminopyridine 149, in which the ring was subsequently closed after treatment with palladium(O) to give the /3-carboline 150. Friedlander condensation of 150 with 2-amino-3-benzyloxy-4-bromo-benzaldehyde (151), which was synthesized in four steps (5S), gave the 2-/3-carbolinequinoline 152. Hydrogen bromide gas debenzoylation of 152 was followed by oxidation with potassium nitrosodisulfonate (Fremy s salt) to obtain Kende s intermediate 131. 

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