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Organic & Biomolecular Chemistry
Journal Name
COMMUNICATION
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corresponding optimized controlled conditions, this alcohol-
based PSRs can selectively afford THBC 3 as well as DHBC 4 or
BC 5 via further aerobic oxidation by O2.
Conclusions
4
In conclusion, the biologically and pharmaceutically significant
tetrahydro-β-carboline and β-carboline scaffolds can now be
selectively obtained by a mild and direct aerobic oxidative
Pictet–Spengler reaction of tryptamines with alcohols in only
one step using TBN/TEMPO as the catalyst, oxygen the oxidant,
and acetic acid a green solvent. This new method is more
advantageous than the known methods for tetrahydro-β-
carboline and β-carboline construction from aldehdyes, not
only because the greener alcohols, transition metal-free
catalyst, and waste-free oxidant O2 can be used, but because
the synthetic and purification processes can be greatly
shortened and simplified, i.e., overall efficiency for
construction of β-carboline scaffolds is greatly enhanced.
Moreover, this method has a relatively broad scope of
substrates, and can be extended to dihydro-β-carboline
synthesis and applied to the more available and more
economic tryptophan. Interestingly, TBN and TEMPO are not
only the oxidation catalyst for the reaction, they are also found
to be capable of facilitating the cyclization of imine
intermediates into the THBC products though the reason was
still remained to be clarified. Further extension and
applications of the TBN/TEMPO-catalyzed aerobic oxidative
cyclocondensation method in construction of other
heterocycle compounds are still in progress in this group.
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Acknowledgements
We thank National Natural Science Foundation of China
(21672163) and Natural Science Foundation of Zhejiang
Province for Distinguished Young Scholars (LR14B020002) for
financial support.
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