Journal of the American Chemical Society
Communication
alkenylative relay Heck and a diastereoselective intramolecular
Diels−Alder reaction, to access these interesting structures.
In summary, we have successfully developed a method to
install electron-deficient alkenyl groups in high enantio-
selectivity at various distances from a resultant carbonyl by
using a redox-relay strategy. The success of this reaction is
attributed to the use of electron-withdrawing alkenyl triflates,
which leads to improved selectivity during the β-hydride
elimination step to reinforce migration of the palladium catalyst
toward the alcohol. This prevents trapping of the catalyst as a
proposed π-allyl species. The relatively mild conditions and
ability to remotely install alkenyl groups to the carbonyl set the
stage for further synthetic applications of this method. Future
work is aimed at this goal and further detailing the mechanistic
underpinnings of this process.
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(
(
7
(
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(13) (a) Liao, L.; Jana, R.; Urkalan, K. B.; Sigman, M. S. J. Am. Chem.
Soc. 2011, 133, 5784. (b) Saini, V.; Sigman, M. S. J. Am. Chem. Soc.
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ASSOCIATED CONTENT
Supporting Information
Experimental procedures and characterization data for new
■
*
S
(
14) For examples of application of chiral pyrox ligands in Pd-
AUTHOR INFORMATION
catalyzed reactions, see: (a) Kikushima, K.; Holder, J. C.; Gatti, M.;
Stoltz, B. M. J. Am. Chem. Soc. 2011, 133, 6902. (b) McDonald, R. I.;
White, P. B.; Weinstein, A. B.; Tam, C. P.; Stahl, S. S. Org. Lett. 2011,
1
3, 2830.
Notes
(
(
(
15) Rauf, W.; Brown, J. M. Chem. Commun. 2013, 49, 8430.
16) Werner, E. W.; Sigman, M. S. J. Am. Chem. Soc. 2011, 133, 9692.
17) Chassaing, S.; Specklin, S.; Weibel, J.-M.; Pale, P. Tetrahedron
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The work was supported by the National Institutes of Health
NIGMS R01GM063540).
■
(
2012, 68, 7245.
(18) The starting materials are generally consumed in the reactions.
The remainder of the mass balance mainly consists of a mixture of
alkene products that are derived from β-insertion into the alkenol.
(
19) Babinski, D.; Soltani, O.; Frantz, D. E. Org. Lett. 2008, 10, 2901.
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