Organic Letters
Letter
(13) Phosphine selenides have previously been employed as catalysts
for the enantioselective transfer of sulfenyl and selenenyl groups to
alkenes: (a) Denmark, S. E.; Hartmann, E.; Kornfilt, D. J. P.; Wang,
H. Mechanistic, Crystallographic, and Computational Studies on the
Catalytic, Enantioselective Sulfenofunctionalization of Alkenes. Nat.
Chem. 2014, 6, 1056−1064. (b) Denmark, S. E.; Chi, H. M. Lewis
Base Catalyzed, Enantioselective, Intramolecular Sulfenoamination of
Olefins. J. Am. Chem. Soc. 2014, 136, 8915−8918. (c) Denmark, S. E.;
Jaunet, A. Catalytic, Enantioselective, Intramolecular Carbosulfenyla-
tion of Olefins. J. Am. Chem. Soc. 2013, 135, 6419−6422.
(d) Denmark, S. E.; Kalyani, D.; Collins, W. R. Preparative and
Mechanistic Studies toward the Rational Development of Catalytic,
Enantioselective Selenoetherification Reactions. J. Am. Chem. Soc.
2010, 132, 15752−15765. (e) Denmark, S. E.; Kornfilt, D. J. P.;
Vogler, T. Catalytic Asymmetric Thiofunctionalization of Unactivated
Alkenes. J. Am. Chem. Soc. 2011, 133, 15308−15311. (f) Denmark, S.
E.; Collins, W. R. Lewis Base Activation of Lewis Acids: Development
of a Lewis Base Catalyzed Selenolactonization. Org. Lett. 2007, 9,
3801−3804.
AUTHOR INFORMATION
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Corresponding Author
ORCID
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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We thank the University of Washington and the National
Science Foundation (CHE-1764450) for funding.
REFERENCES
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(1) Aza-Heck review: Race, N. J.; Hazelden, I. R.; Faulkner, A.;
Bower, J. F. Recent Developments in the Use of Aza-Heck
Cyclizations for the Synthesis of Chiral N-Heterocycles. Chem. Sci.
2017, 8, 5248−5260.
(2) Aza-Wacker review: McDonald, R. I.; Liu, G.; Stahl, S. S.
Palladium(II)-Catalyzed Alkene Functionalization via Nucleopallada-
tion: Stereochemical Pathways and Enantioselective Catalytic
Applications. Chem. Rev. 2011, 111, 2981−3019.
(3) Hosokawa, T.; Takano, M.; Kuroki, Y.; Murahashi, S.-I.
Palladium(II)-Catalyzed Amidation of Alkenes. Tetrahedron Lett.
1992, 33, 6643−6646.
(4) Timokhin, V. I.; Anastasi, N. R.; Stahl, S. S. Dioxygen-Coupled
Oxidative Amination of Styrene. J. Am. Chem. Soc. 2003, 125, 12996−
1997.
(14) Schmidpeter, A.; Brecht, H. Verschiebung der 31P-Resonanz
von Phosphinchalkogoniden in Substitutionsreihen und bei Chalko-
genmethylierung. Z. Naturforsch., B: J. Chem. Sci. 1969, 24, 179−192.
(15) Vummaleti, S. C. C.; Nelson, D. J.; Poater, A.; Gomez-Suarez,
A.; Cordes, D. B.; Slawin, A. M. Z.; Nolan, S. P.; Cavallo, L. What Can
NMR Spectroscopy of Selenoureas and Phosphinidenes Teach Us
about the π-Accepting Abilities of N-Heterocyclic Carbenes? Chem.
Sci. 2015, 6, 1895−1904.
(16)
(5) Brice, J. L.; Harang, J. E.; Timokhin, V. I.; Anastasi, N. R.; Stahl,
S. S. Aerobic Oxidative Amination of Unactivated Alkenes Catalyzed
by Palladium. J. Am. Chem. Soc. 2005, 127, 2868−2869.
(6) Rogers, M. M.; Kotov, V.; Chatwichien, J.; Stahl, S. S. Palladium-
Catalyzed Oxidative Amination of Alkenes: Improved Catalyst
Reoxidation Enables the Use of Alkene as the Limiting Reagent.
Org. Lett. 2007, 9, 4331−4334.
(7) Liu, G.; Yin, G.; Wu, L. Palladium-Catalyzed Intermolecular
Aerobic Oxidative Amination of Terminal Alkenes: Efficient Synthesis
of Linear Allylamine Derivatives. Angew. Chem., Int. Ed. 2008, 47,
4733−4736.
(17) (a) Aragoni, M. C.; Arca, M.; Demartin, F.; Devillanova, F. A.;
Garau, A.; Grimaldi, P.; Isaia, F.; Lelj, F.; Lippolis, V.; Verani, G. First
ICN Adduct with a Selenium Donor (R = Se): Is It an Ionic
[RSeCN]+I− or a “T-Shaped” R(I)SeCN Hypervalent Compound?
Eur. J. Inorg. Chem. 2004, 2004, 2363−2368. (b) Godfrey, S. M.;
Jackson, S. L.; McAuliffe, C. A.; Pritchard, R. G. Reaction of Tertiary
Phosphine Selenides, R3PSe (R = Me2N, Et2N or C6H11), with
Dibromine. The First Reported Examples of 1:1 Addition. J. Chem.
Soc., Dalton Trans. 1998, 4201−4204.
(18) Kwart, L. D.; Horgan, A. G.; Kwart, H. Structure of the
Reaction Barrier in the Selenoxide-Mediated Formation of Olefins. J.
Am. Chem. Soc. 1981, 103, 1232−1234.
(8) Copper can promote a similar reaction for a limited selection of
styrenes: Liwosz, T. W.; Chemler, S. R. Copper-Catalyzed Oxidative
Amination and Allylic Amination of Alkenes. Chem. - Eur. J. 2013, 19,
12771−12777.
(19) The isotope effect measured by the competition experiment in
Scheme 5 is not exactly the same as that measured by labeling in
Scheme 3 because neither experiment measures a pure single-step
isotope effect for the elimination step. The labeling experiment
incorporates a secondary isotope effect in the elimination of a proton,
while the competition experiment may incorporate some of the
secondary deuterium isotope effect from the addition steps.
(20) (a) Denney, D. B.; Tunkel, N. Deuterium Isotope Effects
During Additions to Deuteriated and Nondeuteriated Olefins. Chem.
(9) The regioselectivity of the elimination step can be controlled by
choosing substrates that will isomerize to a single thermodynamically
preferred product; see: Kohler, D. G.; Gockel, S. N.; Kennemur, J. L.;
Waller, P. J.; Hull, K. L. Palladium-catalysed Anti-Markovnikov
Selective Oxidative Amination. Nat. Chem. 2018, 10, 333−340.
(10) Though it does not proceed via an aza-Wacker mechanism, Pd-
catalyzed allylic amination via a π-allyl intermediate gives the same
product; see: Pattillo, C. C.; Strambeanu, I. I.; Calleja, P.; Vermeulen,
N. A.; Mizuno, T.; White, M. C. Aerobic Linear Allylic C−H
Amination: Overcoming Benzoquinone Inhibition. J. Am. Chem. Soc.
2016, 138, 1265−1272 and references therein .
2
Ind. 1959, 1383. (b) Merrigan, S. R.; Singleton, D. A. 13C and H
Kinetic Isotope Effects and the Mechanism of Bromination of 1-
Pentene under Synthetic Conditions. Org. Lett. 1999, 1, 327−329.
(11) Trenner, J.; Depken, C.; Weber, T.; Breder, A. Direct Oxidative
Allylic and Vinylic Amination of Alkenes through Selenium Catalysis.
Angew. Chem., Int. Ed. 2013, 52, 8952−8956. Ortgies, S.; Breder, A.
Selenium-Catalyzed Oxidative C(sp2)−H Amination of Alkenes
Exemplified in the Expedient Synthesis of (Aza-)Indoles. Org. Lett.
2015, 17, 2748−2751.
(12) Deng, Z.; Wei, J.; Liao, L.; Huang, H.; Zhao, X. Organo-
selenium-Catalyzed, Hydroxy-Controlled Regio- and Stereoselective
Amination of Terminal Alkenes: Efficient Synthesis of 3-Amino Allylic
Alcohols. Org. Lett. 2015, 17, 1834−1837. Zhang, X.; Guo, R.; Zhao,
X. Organoselenium-catalyzed Synthesis of Indoles through Intra-
molecular C−H Amination. Org. Chem. Front. 2015, 2, 1334−1337.
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