Organic Letters
Letter
ORCID
Scheme 4. Possible Reaction Pathways between Grignard
Reagent 2a and Vinyl Ether 3o
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We are grateful for generous financial support from the
General Medical Sciences of the National Institutes of Health
(GM083944-08).
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Scheme 5. Reaction of Grignard Reagent 2a with Alkynes 17
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In summary, we have developed a highly effective oxidative
Heck reaction of readily available Grignard reagents with
Pd(OAc)2 as the catalyst and di-t-butyldiaziridinone (1) as the
oxidant. Various terminal and internal olefins can react with
Grignard reagents under mild conditions to give the corre-
sponding substituted olefins in 46−91% yields with generally
high regioselectivity. Sterically congested tetrasubstituted olefins
can also be readily formed with internal alkynes. To the best of
our knowledge, this work represents the first Pd-catalyzed oxida-
tive Heck reaction with Grignard reagents. The ready availability
of Grignard reagents along with the high activity of the reaction
system could make the current process synthetically useful.
Further development of the reaction process will be pursued.
ASSOCIATED CONTENT
* Supporting Information
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S
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16496. (q) He, Z.; Kirchberg, S.; Frohlich, R.; Studer, A. Angew.
Chem., Int. Ed. 2012, 51, 3699. (r) Mei, T.-S.; Werner, E. W.; Burckle,
A. J.; Sigman, M. S. J. Am. Chem. Soc. 2013, 135, 6830. (s) Alamsetti,
The Supporting Information is available free of charge on the
̈
S. K.; Persson, A.K.Å.; Jiang, T.; Backvall, J.-E. Angew. Chem., Int. Ed.
Experimental procedures, characterization data for
compounds, and NMR spectra (PDF)
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AUTHOR INFORMATION
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