Organic Letters
Letter
Alkenes by Sequential Isomerization/Cross-Coupling Reactions. J. Am.
Chem. Soc. 2018, 140, 4743−4750.
allyl amines using the readily available Crabtree’s catalyst. Of
note, activation with hydrogen was not required, and the
reaction was performed in mild conditions and with low catalyst
loading (usually 1 mol %). The catalytic species as well as a
detailed reaction mechanism were studied by DFT calculations.
This novel transformation provides a new strategy for the
synthesis of complex amines.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
Garcon, M.; Verdaguer, X.; Riera, A. Total Synthesis of (R)-Sarkomycin
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S
Methyl Ester via Regioselective Intermolecular Pauson−Khand
Reaction and Iridium-Catalyzed Asymmetric Isomerization. Org. Lett.
2018, 20, 3953−3957.
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Characterization of all new compounds. NMR experi-
ments. Experimental and computational details. Energy
profiles, Cartesian coordinates and energies of all
optimized structures(PDF)
AUTHOR INFORMATION
Corresponding Authors
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ORCID
(5) Larionov, E.; Li, H.; Mazet, C. Well-Defined Transition Metal
Hydrides in Catalytic Isomerizations. Chem. Commun. 2014, 50, 9816−
9826.
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(6) Meinwald, J.; Labana, S. S.; Chadha, M. S. Peracid Reactions. III.
The Oxidation of Bicyclo [2.2.1 ]Heptadiene. J. Am. Chem. Soc. 1963,
85, 582−585.
Author Contributions
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(7) Karame, I.; Tommasino, M. L.; Lemaire, M. Iridium-Catalyzed
A.C. did the experimental work. G.S. and G.U. perform the
theoretical calculations. X.V., A.L., and A. R. directed the work
and wrote the article.
Alternative of the Meinwald Rearrangement. Tetrahedron Lett. 2003,
44, 7687−7689.
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́
(8) Vyas, D. J.; Larionov, E.; Besnard, C.; Guenee, L.; Mazet, C.
Isomerization of Terminal Epoxides by a [Pd-H] Catalyst: A Combined
Experimental and Theoretical Mechanistic Study. J. Am. Chem. Soc.
2013, 135, 6177−6183.
Notes
The authors declare no competing financial interest.
(9) Humbert, N.; Vyas, D. J.; Besnard, C.; Mazet, C. An Air-Stable
Cationic Iridium Hydride as a Highly Active and General Catalyst for
the Isomerization of Terminal Epoxides. Chem. Commun. 2014, 50, 1−
4.
ACKNOWLEDGMENTS
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We thank institutional funding from the Spanish Ministry of
Economy, Industry and Competitiveness (MINECO,
CTQ2017-87840-P and CTQ2017-87889-P) through the
Centres of Excellence Severo Ochoa award, and from the
CERCA Programme of the Catalan Government. A.C. and G.S.
thank MINECO and UAB for Ph.D. fellowships (FPU and
UAB-PIF).
(10) Zhang, Z. Da; Scheffold, R. Asymmetric Catalysis by Vitamin
B12: The Isomerization of Achiral Aziridines to Optically Active Allylic
Amines. Helv. Chim. Acta 1993, 76, 2602−2615.
(11) Sugihara, Y.; Iimura, S.; Nakayama, J. Aza-Pinacol Rearrange-
ment: Acid-Catalyzed Rearrangement of Aziridines to Imines. Chem.
Commun. 2002, 134−135.
(12) Wolfe, J. P.; Ney, J. E. A New, Mild Synthesis of N-Sulfonyl
Ketimines via the Palladium-Catalyzed Isomerization of Aziridines.
Org. Lett. 2003, 5, 4607−4610.
ABBREVIATIONS
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p-Tol, 4-methylphenyl; Ts, tosyl, p-toluensulfonyl; Cy, cyclo-
hexyl; Ph, phenyl; BArF, tetrakis[3,5-bis(trifluoromethyl)-
phenyl]borate; DFT, density functional theory
(13) (a) Kiyokawa, K.; Kojima, T.; Hishikawa, Y.; Minakata, S. Iodine-
Catalyzed Decarboxylative Amidation of Β,γ-Unsaturated Carboxylic
Acids with Chloramine Salts Leading to Allylic Amides. Chem. - Eur. J.
2015, 21, 15548−15552. (b) Verendel, J. J.; Zhou, T.; Li, J. Q.;
Paptchikhine, A.; Lebedev, O.; Andersson, P. G. Highly Flexible
Synthesis of Chiral Azacycles via Iridium-Catalyzed Hydrogenation. J.
Am. Chem. Soc. 2010, 132, 8880−8881. (c) Feng, J.; Wang, Y.; Li, Q.;
Jiang, R.; Tang, Y. Facile Synthesis of Pyrroles via Rh(II)-Catalyzed
Transannulation of 1-Tosyl-1,2,3-Triazoles with Silyl or Alkyl Enol
Ethers. Tetrahedron Lett. 2014, 55, 6455−6458. (d) Meng, K.; Xia, J.;
Wang, Y.; Zhang, X.; Yang, G.; Zhang, W. Ir/BiphPHOX-Catalyzed
Asymmetric Hydrogenation of 3-Substituted 2,5-Dihydropyrroles and
2,5-Dihydrothiophene 1,1-Dioxides. Org. Chem. Front. 2017, 4, 1601−
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