Organic Letters
Letter
WOG), and the Hercules Foundation. The authors thank Prof.
Christophe Vande Velde (University of Antwerp) for
thermogravimetric analysis.
Scheme 5. Addition of Grignard Reactants (2f, 2o) to S-
Phenyl tert-Butylthiocarbamate (1b) using tert-
Butylmagnesium Chloride as a Sacrificial Base
DEDICATION
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This work is dedicated to Prof. Gordon W. Gribble on the
occasion of his retirement from Dartmouth College in
recognition of his outstanding scientific achievements, educa-
tional commitment, and service to the heterocyclic chemistry
community.
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Finally, this modified procedure was also successfully applied
for the synthesis of N-tert-butylbenzamide (3f) using a
combination of less sterically hindered phenylmagnesium
t
bromide (2f) and BuMgCl.
In summary, we have demonstrated that secondary amides
can be obtained from easily accessible thiocarbamates and
t
Grignard reactants. A combination of BuMgCl as a sacrificial
base with only 1 equiv of Grignard reactant can also be used
when the latter is expensive. This protocol allows the synthesis
of (sterically and electronically) challenging amides, which are
not or hardly accessible via classical approaches. Recovery of
the thiophenolate leaving group from S-phenyl thiocarbamate
substrates as diphenyl disulfide reduces waste production, as
diphenyl disulfide is readily transformed into S-phenyl
benzenethiosulfonate, which is a reactant for the three-
component reaction yielding S-phenyl thiocarbamate sub-
strates.
ASSOCIATED CONTENT
* Supporting Information
■
S
The Supporting Information is available free of charge on the
Classical coupling reagents, thermogravimetric analysis,
experimental procedures, characterization of new com-
pounds and spectral data (PDF)
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Corresponding Author
ORCID
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All of the authors have approved the final version of the
manuscript.
Notes
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The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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This research was financially supported by the University of
Antwerp (BOF, IOF), the Research Foundation-Flanders
(FWO) (Ph.D. fellowship to P.M., research project and
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