Organic Letters
Letter
(3) Taylor, R. D.; MacCoss, M.; Lawson, A. D. G. Rings in Drugs. J.
Med. Chem. 2014, 57, 5845−5859.
Houk, K. N.; Snieckus, V.; Garg, N. K. J. Am. Chem. Soc. 2011, 133,
6352−6363. (g) Silberstein, A.; Ramgren, S. D.; Garg, N. K. Iron-
Catalyzed Alkylations of Aryl Sulfamates and Carbamates. Org. Lett.
2012, 14, 3796−3799. (h) Ackermann, L.; Sandmann, R.; Song, W.
Palladium- and Nickel-Catalyzed Aminations of Aryl Imidazolylsulfo-
nates and Sulfamates. Org. Lett. 2011, 13, 1784−1786. (i) Molander,
G. A.; Shin, I. Pd-Catalyzed Suzuki−Miyaura Cross-Coupling
Reactions between Sulfamates and Potassium Boc-Protected Amino-
methyltrifluoroborates. Org. Lett. 2013, 15, 2534−2537. (j) Takise,
R.; Itami, K.; Yamaguchi, J. Cyanation of Phenol Derivatives with
Aminoacetonitriles by Nickel Catalysis. Org. Lett. 2016, 18, 4428−
4431. (k) Melvin, P. R.; Hazari, N.; Beromi, M. M.; Shah, H. P.;
Williams, M. J. Pd-Catalyzed Suzuki-Miyaura and Hiyama-Denmark
Couplings of Aryl Sulfamates. Org. Lett. 2016, 18, 5784−5787.
(l) Kuriyama, M.; Kujirada, S.; Tsukuda, K.; Onomura, O. Nickel-
Catalyzed Deoxygenative Deuteration of Aryl Sulfamates. Adv. Synth.
Catal. 2017, 359, 1043−1048. (m) Gan, Y.; Wang, G.; Xie, X.; Liu, Y.
Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2
Involving C−O Bond Cleavage. J. Org. Chem. 2018, 83, 14036−
14048. (n) Coombs, J. R.; Green, R. A.; Roberts, F.; Simmons, E. M.;
Stevens, J. M.; Wisniewski, S. R. Advances in Base-Metal Catalysis:
Development of a Screening Platform for Nickel-Catalyzed
Borylations of Aryl (Pseudo)halides with B2(OH)4. Organometallics
2019, 38, 157−166.
(9) For seminal reports on nickel-catalyzed C−N coupling reactions,
see: (a) Wolfe, J. P.; Buchwald, S. L. Nickel-Catalyzed Amination of
Aryl Chlorides. J. Am. Chem. Soc. 1997, 119, 6054−6058. (b) Brenner,
E.; Fort, Y. New Efficient Nickel(0) Catalysed Amination of Aryl
Chlorides. Tetrahedron Lett. 1998, 39, 5359−5362. For a recent
review, see: (c) Marín, M.; Rama, R. J.; Nicasio, M. C. Ni-Catalyzed
Amination Reactions: An Overview. Chem. Rec. 2016, 16, 1819−1832.
(10) (a) Koo, K.; Hillhouse, G. L. Carbon-Nitrogen Bond
Formation by Reductive Elimination From Nickel(II) Amido Alkyl
Complexes. Organometallics 1995, 14, 4421−4423. (b) Ilies, L.;
Matsubara, T.; Nakamura, E. Nickel-Catalyzed Synthesis of Diaryl-
amines via Oxidatively Induced C−N Bond Formation at Room
Temperature. Org. Lett. 2012, 14, 5570−5573.
(11) (a) Corcoran, E. B.; Pirnot, M. T.; Lin, S.; Dreher, S. D.;
DiRocco, D. A.; Davies, I. W.; Buchwald, S. L.; MacMillan, D. W. C.
Aryl Amination Using Ligand-Free Ni(II) Salts and Photoredox
Catalysis. Science 2016, 353, 279−283. (b) Oderinde, M. S.; Jones, N.
H.; Juneau, A.; Frenette, M.; Aquila, B.; Tentarelli, S.; Robbins, D. W.;
Johannes, J. W. Highly Chemoselective Iridium Photoredox and
Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with
Aryl Halides. Angew. Chem., Int. Ed. 2016, 55, 13219−13223. (c) Key,
R. J.; Vannucci, A. K. Nickel Dual Photoredox Catalysis for the
Synthesis of Aryl Amines. Organometallics 2018, 37, 1468−1472.
(d) Kim, T.; McCarver, S. J.; Lee, C.; MacMillan, D. W. C.
Sulfonamidation of Aryl and Heteroaryl Halides through Photo-
sensitized Nickel Catalysis. Angew. Chem., Int. Ed. 2018, 57, 3488−
3452. (e) Reddy, L. R.; Kotturi, S.; Waman, Y.; Ravinder Reddy, V.;
Patel, C.; Kobarne, A.; Kuttappan, S. N-Arylation of Carbamates
through Photosensitized Nickel Catalysis. J. Org. Chem. 2018, 83,
13854−13860. (f) Konev, M. O.; McTeague, T. A.; Johannes, J. W.
Nickel-Catalyzed Photoredox-Mediated Cross-Coupling of Aryl
Electrophiles and Aryl Azides. ACS Catal. 2018, 8, 9120−9124.
(12) DBU has previously found use in electrochemically enabled,
nickel-catalyzed C−N couplings. See: (a) Li, C.; Kawamata, Y.;
Nakamura, H.; Vantourout, J. C.; Liu, Z.; Hou, Q.; Bao, D.; Starr, J.
T.; Chen, J.; Yan, M.; Baran, P. S. Electrochemically Enabled, Nickel-
Catalyzed Amination. Angew. Chem., Int. Ed. 2017, 56, 13088−13093.
(b) Kawamata, Y.; Vantourout, J. C.; Hickey, D. P.; Bai, P.; Chen, L.;
Hou, Q.; Qiao, W.; Barman, K.; Edwards, M. A.; Garrido-Castro, A.
F.; deGruyter, J. N.; Nakamura, H.; Knouse, K.; Qin, C.; Clay, K. J.;
Bao, D.; Li, C.; Starr, J. T.; Garcia-Irizarry, C.; Sach, N.; White, H. S.;
Neurock, M.; Minteer, S. D.; Baran, P. S. Electrochemically Driven,
Ni-Catalyzed Aryl Amination: Scope, Mechanism, and Applications. J.
Am. Chem. Soc. 2019, 141, 6392−6402.
(4) For recent examples of the utility of N-substituted sulfamate
esters, see: (a) Short, M. A.; Blackburn, J. M.; Roizen, J. L. Sulfamate
Esters Guide Selective Radical-Mediated Chlorination of Aliphatic
C−H Bonds. Angew. Chem., Int. Ed. 2018, 57, 296−299.
(b) Sathyamoorthi, S.; Banerjee, S.; Du Bois, J.; Burns, N. Z.; Zare,
R. N. Site-Selective Bromination of sp3C−H Bonds. Chem. Sci. 2018,
9, 100−104. (c) Ayer, S. K.; Roizen, J. L. Sulfamate Esters Guide
C(3)-Selective Xanthylation of Alkanes. J. Org. Chem. 2019, 84,
3508−3523. (d) Del Castillo, E.; Martìnez, M. D.; Bosnidou, A. E.;
́
Duhamel, T.; O’Broin, C. Q.; Zhang, H.; Escudero-Adan, E. C.;
Martínez-Belmonte, M.; Muniz, K. Chem. - Eur. J. 2018, 24, 17225−
̃
17229. (e) Ma, Z.-Y.; Guo, L.-N.; You, Y.; Yang, F.; Hu, M.; Duan, X.-
H. Visible Light Driven Alkylation of C(sp3)−H Bonds Enabled by
1,6-Hydrogen Atom Transfer/Radical Relay Addition. Org. Lett. 2019,
21, 5500−5504. (f) Kanegusuku, A. L. G.; Castanheiro, T.; Ayer, S.
K.; Roizen, J. L. Sulfamyl Radicals Direct Photoredox-Mediated Giese
Reactions at Unactivated C(3)−H Bonds. Org. Lett. 2019, 21, 6089−
6095. (g) Shu, W.; Zhang, H.; Huang, Y. γ-Alkylation of Alcohols
Enabled by Visible-Light Induced 1,6-Hydrogen Atom Transfer. Org.
Lett. 2019, 21, 6107−6111.
(5) For a recent overview, see: Bariwal, J.; Van der Eycken, E. C−N
Bond Forming Cross-Coupling Reactions: An Overview. Chem. Soc.
Rev. 2013, 42, 9283−9303.
(6) For a recent review, see: Ruiz-Castillo, P.; Buchwald, S. L.
Applications of Palladium-Catalyzed C−N Cross-Coupling Reactions.
Chem. Rev. 2016, 116, 12564−12649.
(7) For early reports on the use of sulfonamides, amides, carbamates,
and sulfamides in palladium-mediated Buchwald−Hartwig amination
reactions, see: (a) Hartwig, J. F.; Kawatsura, M.; Hauck, S. I.;
Shaughnessy, K. H.; Alcazar-Roman, L. M. Room-Temperature
Palladium-Catalyzed Amination of Aryl Bromides and Chlorides
and Extended Scope of Aromatic C−N Bond Formation with a
Commercial Ligand. J. Org. Chem. 1999, 64, 5575−5580. (b) Yin, J.;
Buchwald, S. L. Palladium-Catalyzed Intermolecular Coupling of Aryl
Halides and Amides. Org. Lett. 2000, 2, 1101−1104. (c) Alcaraz, L.;
Bennion, C.; Morris, J.; Meghani, P.; Thom, S. M. Novel N-Aryl and
N-Heteroaryl Sulfamide Synthesis via Palladium Cross Coupling. Org.
Lett. 2004, 6, 2705−2708. For selected recent improvements, see:
(d) Rosen, B. R.; Ruble, J. C.; Beauchamp, T. J.; Navarro, A. Mild Pd-
Catalyzed N-Arylation of Methanesulfonamide and Related Nucleo-
philes: Avoiding Potentially Genotoxic Reagents and Byproducts. Org.
Lett. 2011, 13, 2564−2567. (e) Crawford, S. M.; Lavery, C. B.;
Stradiotto, M. Bippyphos: A Single Ligand with Unprecedented Scope
in the Buchwald−Hartwig Amination of (Hetero)aryl Chlorides.
Chem. - Eur. J. 2013, 19, 16760−16771. (f) Lavoie, C. M.; MacQueen,
P. M.; Stradiotto, M. Nickel-Catalyzed N-Arylation of Primary
Amides and Lactams with Activated (Hetero)aryl Electrophiles.
Chem. - Eur. J. 2016, 22, 18752−18755.
(8) For seminal examples detailing the use of sulfamate esters as
electrophiles in transition metal-catalyzed coupling processes, see:
(a) Macklin, T. K.; Snieckus, V. Directed Ortho Metalation
Methodology. The N,N-Dialkyl Aryl O-Sulfamate as New Directed
Metalation Group and Cross-Coupling Partner for Grignard Reagents.
Org. Lett. 2005, 7, 2519−2522. (b) Wehn, P. M.; Du Bois, J.
Exploring New Uses for C−H Amination: Ni-Catalyzed Cross-
Coupling of Cyclic Sulfamates. Org. Lett. 2005, 7, 4685−4688. For
selected advances in the use of sulfamate ester electrophiles, see:
(c) Quasdorf, K. W.; Riener, M.; Petrova, K. V.; Garg, N. K. Suzuki−
Miyaura Coupling of Aryl Carbamates, Carbonates, and Sulfamates. J.
Am. Chem. Soc. 2009, 131, 17748−17749. (d) Mesganaw, T.;
Silberstein, A. L.; Ramgren, S. D.; Nathel, N. F.; Hong, X.; Liu, P.;
Garg, N. K. Nickel-Catalyzed Amination of Aryl Carbamates and
Sequential Site-Selective Cross-Couplings. Chem. Sci. 2011, 2, 1766−
1771. (e) Ramgren, S. D.; Silberstein, A. L.; Yang, Y.; Garg, N. K.
Nickel-Catalyzed Amination of Aryl Sulfamates. Angew. Chem., Int. Ed.
2011, 50, 2171−2173. (f) Quasdorf, K. W.; Antoft-Finch, A.; Liu, P.;
Silberstein, A. L.; Komaromi, A.; Blackburn, T.; Ramgren, S. D.;
E
Org. Lett. XXXX, XXX, XXX−XXX