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Journal of the American Chemical Society
(4) During the preparation of this manuscript, a copper-catalyzed
ASSOCIATED CONTENT
enantioselective three-component carboamination of styrenes with
N-fluoro sulfonamides and aryl boronic acids was reported: Wang, D.; Wu,
L.; Wang, F.; Wan, X.; Chen, P.; Lin, Z.; Liu, G. J. Am. Chem. Soc. 2017,
139, 6811–6814.
(5) Gurak, J. A., Jr.; Yang, K. S.; Liu, Z.; Engle, K. M. J. Am. Chem. Soc.
2016, 138, 5805–5808.
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Supporting Information
Experiment details, spectra data, copies of 1H and 13C NMR spectra,
X-ray crystallographic data, and computational details. These materials
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(6) Yang, K. S.; Gurak, J. A., Jr.; Liu, Z.; Engle, K. M. J. Am. Chem. Soc.
2016, 138, 14705–14712.
AUTHOR INFORMATION
(7) Liu, Z.; Zeng, T.; Yang, K. S.; Engle, K. M. J. Am. Chem. Soc. 2016, 138,
15122–15125.
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Corresponding Author
* E-mail: pengliu@pitt.edu, keary@scripps.edu
(8) For reviews on high-valent palladium in catalysis, see: (a) Muñiz, K.
Angew. Chem. Int. Ed. 2009, 48, 9412–9423. (b) Canty, A. J. Dalton. Trans.
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49, 2413–2423. For other directing group approaches to alkene
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4101–4104.
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D.; Daugulis, O. J. Am. Chem. Soc. 2005, 127, 13154–13155. (b) Shabashov,
D.; Daugulis, O. J. Am. Chem. Soc. 2010, 132, 3965–3972. (c) Ano, Y.;
Tobisu, M.; Chatani, N. J. Am. Chem. Soc. 2011, 133, 12984–12986. (d)
Gutekunst, W. R.; Baran, P. S. J. Org. Chem. 2014, 79, 2430–2452. For
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aminocarbonylation of alkenes, see: (a) Cheng, J.; Qi, X.; Li, M.; Chen, P.;
Liu, G. J. Am. Chem. Soc. 2015, 137, 2480–2483. For intermolecular
carboazidation of alkenes, see: (b) Weidner, K.; Giroult, A.; Panchaud, P.;
Renaud, P. J. Am. Chem. Soc. 2010, 132, 17511–17515. For intermolecular
aminocyanation of alkenes, see: (c) Zhang, H.; Pu, W.; Xiong, T.; Li, Y.;
Zhou, X.; Sun, K.; Liu, Q.; Zhang, Q. Angew. Chem. Int. Ed. 2013, 52,
2529–2533.
(11) This alkene Z/E isomerization phenomenon was previously observed
in a C–H alkenylation reaction: Shan, G.; Huang, G.; Rao, Y. Org. Biomol.
Chem. 2015, 13, 697–701. In this report, the authors proposed a Z/E
isomerization pathway via an Pd(IV)-π-benzyl-type intermediate when
using (Z)-styrenyl iodide as the electrophile. However, this model cannot
explain the isomerization of (Z)-alkenyl iodide bearing an alkyl group (for
example 4j in the present work). We have found that when Z-alkenyl
iodides are employed in the reaction, the corresponding E isomer is not
observed under the reaction conditions. We have further established that
reaction rates with E- and Z-alkenyl iodides are similar (with in a factor of
2), which is inconsistent with a scenario in which the Z-isomer is converted
to E, which in turn reacts with a sufficiently high rate such that it cannot be
detected. Beyond these preliminary insights, the mechanism by which
Z/E-isomerization takes place remains unclear.
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Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was financially supported by TSRI, Pfizer, Inc and the NSF
(CHE-1654122). We gratefully acknowledge the Nankai University
College of Chemistry for an International Research Scholarship
(Z.W.). We thank Prof. Donna G. Blackmond for guidance with RPKA
experiments, Dr. Milan Gembicky (UCSD) for X-ray crystallographic
analysis, and Dr. Zachary K. Wickens (Harvard University) for helpful
discussion. Materia, Inc. is acknowledged for generous donation of
Hoveyda–Grubbs second-generation catalyst. We thank the NSF
XSEDE for supercomputer resources.
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