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ChemComm
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DOI: 10.1039/C7CC00555E
COMMUNICATION
Journal Name
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Figure 3 a) Circular dichroism spectra of oxidized c(Pro-Trp) DKPs 4g-i in
MeOH. Chiral HPLC profiles of compounds b) 4g from 1g; c) 4h from 1h; d)
co-injection of 4g and 4h from 1g and 1h, respectively; e) 4h from 1i.
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In circular dichroism measurements in MeOH (Fig. 3a), the
product 4g from the L-Pro-L-Trp DKP (1g) showed a positive
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L-Pro-D-Trp
(1h and 1i, respectively) displayed identical
profiles, opposite to compound 4g (Fig. 3a). Additionally, chiral
HPLC analysis (Fig. 3b-e, see SI for details) positively support
this relationship and demonstrate the retention of
configuration at the Trp stereogenic centre.
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In summary we have disclosed novel oxidative couplings for
the selective formation of C-C and C-N bonds on unprotected
Trp-DKPs in a straightforward manner. In these reactions, the
cyclization step prevails over the routine dehydrogenations or
hydrolytic degradations and gives direct access to fused and
bridged DKP chemotypes with relevant presence in medicinal
and natural product chemistry. These results represent a
significant expansion of the scope of selective oxidative
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L. M.-T. acknowledges the support of MECD- Spain for a FPU
Scholarship. We thank the funding of DGICYT-Spain (CTQ2015-
67870-P) and Generalitat de Catalunya (2014 SGR 137).
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4 | J. Name., 2012, 00, 1-3
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