Organic Letters
Letter
Highly Diastereo- and Enantioselective Intramolecular Amidation of
Saturated C−H Bonds Catalyzed by Ruthenium Porphyrins. Angew.
Chem., Int. Ed. 2002, 41, 3465−3468. (k) Milczek, E.; Boudet, N.;
Blakey, S. Enantioselective C−H Amination Using Cationic
Ruthenium(II)−pybox Catalysts. Angew. Chem., Int. Ed. 2008, 47,
6825−6828. (l) Liang, J.-L.; Yuan, S.-X.; Huang, J.-S.; Che, C.-M.
Intramolecular C-N Bond Formation Reactions Catalyzed by
Ruthenium Porphyrins: Amidation of Sulfamate Esters and
Aziridination of Unsaturated Sulfonamides. J. Org. Chem. 2004, 69,
3610−3619. (m) Li, Z.; He, C. Recent Advances in Silver-Catalyzed
Nitrene, Carbene, and Silylene-Transfer Reactions. Eur. J. Org. Chem.
2006, 2006, 4313−4322. (n) Alderson, J. M.; Corbin, J. R.;
Schomaker, J. M. Tunable, Chemo- and Site-Selective Nitrene
Transfer Reactions through the Rational Design of Silver(I) Catalysts.
Acc. Chem. Res. 2017, 50, 2147−2158. (o) Hong, S. Y.; Park, Y.;
Hwang, Y.; Kim, Y. B.; Baik, M.-H.; Chang, S. Selective formation of
g-lactams via C−H amidation enabled by tailored iridium catalysts.
Science 2018, 359, 1016.
(7) (a) Yan, S.-Y.; Wang, Y.; Shu, Y.-J.; Liu, H.-H.; Zhou, X.-G.
Nitrene Transfer Reaction Catalyzed by Substituted Metallophthalo-
cyanines. J. Mol. Catal. A: Chem. 2006, 248, 148−151. (b) Liu, Y.;
Che, C.-M. [FeIII(F20-tpp)Cl] Is an Effective Catalyst for Nitrene
Transfer Reactions and Amination of Saturated Hydrocarbons with
Sulfonyl and Aryl Azides as Nitrogen Source under Thermal and
Microwave-Assisted Conditions. Chem. - Eur. J. 2010, 16, 10494−
10501. (c) Wang, Z.; Zhang, Y.; Fu, H.; Jiang, Y.; Zhao, Y. Efficient
Intermolecular Iron-Catalyzed Amidation of C-H Bonds in the
Presence of N-Bromosuccinimide. Org. Lett. 2008, 10, 1863−1866.
(d) Enthaler, S.; Junge, K.; Beller, M. Sustainable Metal Catalysis with
Iron: From Rust to a Rising Star? Angew. Chem., Int. Ed. 2008, 47,
3317−3321. (e) Karimov, R. R.; Sharma, A.; Hartwig, J. F. Late Stage
Azidation of Complex Molecules. ACS Cent. Sci. 2016, 2, 715−724.
(f) Sharma, A.; Hartwig, J. F. Metal-Catalysed Azidation of Tertiary
C−H Bonds Suitable for Late-Stage Functionalization. Nature 2015,
517, 600−604. (g) Wang, H.; Li, Y.; Wang, Z.; Lou, J.; Xiao, Y.; Qiu,
G.; Hu, X.; Altenbach, H.-J.; Liu, P. Iron-catalyzed efficient
intermolecular amination of C(sp3)−H bonds with bromamine-T as
nitrene source. RSC Adv. 2014, 4, 25287−25290.
1, 1400−1401. (b) Breslow, R.; Gellman, S. H. Intramolecular
Nitrene C−H Insertions Mediated by Transition-Metal Complexes as
Nitrogen Analogues of Cytochrome P-450 Reactions. J. Am. Chem.
Soc. 1983, 105, 6728−6729.
(11) Paradine, S. M.; White, M. C. Iron-Catalyzed Intramolecular
Allylic C−H Amination. J. Am. Chem. Soc. 2012, 134, 2036−2039.
(12) Liu, Y.; Guan, X.; Wong, E. L.-M.; Liu, P.; Huang, J.-S.; Che,
C.-M. Nonheme Iron-Mediated Amination of C(sp3)−H Bonds.
Quinquepyridine-Supported Iron-Imide/Nitrene Intermediates by
Experimental Studies and DFT Calculations. J. Am. Chem. Soc.
2013, 135, 7194−7204.
(13) Selected examples: (a) Hennessy, E. T.; Betley, T. A. Complex
N-Heterocycle Synthesis via Iron-Catalyzed, Direct C−H Bond
Amination. Science 2013, 340, 591−595. (b) Bagh, B.; Broere, D. L.
J.; Sinha, V.; Kuijpers, P. F.; Van Leest, N. P.; De Bruin, B.;
Demeshko, S.; Siegler, M. A.; Van Der Vlugt, J. I. Catalytic Synthesis
of N−Heterocycles via Direct C(sp3)−H Amination Using an Air-
Stable Iron(III) Species with a Redox-Active Ligand. J. Am. Chem. Soc.
2017, 139, 5117−5124. (c) Alt, I. T.; Guttroff, C.; Plietker, B. Iron-
Catalyzed Intramolecular Aminations of C(sp3)−H Bonds in
Alkylaryl Azides. Angew. Chem., Int. Ed. 2017, 56, 10582−10586.
(d) Shing, K.-P.; Liu, Y.; Cao, B.; Chang, X.-Y.; You, T.; Che, C.-M.
N-Heterocyclic Carbene Iron(III) Porphyrin-Catalyzed Intramolecu-
lar C(sp3)−H Amination of Alkyl Azides. Angew. Chem., Int. Ed. 2018,
57, 11947−119511.
(14) For selected examples using aminopyridine ligands in iron-
catalyzed oxidation reactions, see: (a) Chen, M. S.; White, M. C. A
Predictably Selective Aliphatic C−H Oxidation Reaction for Complex
́
Molecule Synthesis. Science 2007, 318, 783−787. (b) Cusso, O.;
Cianfanelli, M.; Ribas, X.; Klein Gebbink, R. J. M.; Costas, M. Iron
Catalyzed Highly Enantioselective Epoxidation of Cyclic Aliphatic
Enones with Aqueous H2O2. J. Am. Chem. Soc. 2016, 138, 2732−
2738. (c) Chen, M. S.; White, M. C. Combined Effects on Selectivity
in Fe-Catalyzed Methylene Oxidation. Science 2010, 327, 566−571.
(d) Kal, S.; Draksharapu, A.; Que, L., Jr. Sc3+ (or HClO4) Activation
of a Nonheme FeIII−OOH Intermediate for the Rapid Hydroxylation
of Cyclohexane and Benzene. J. Am. Chem. Soc. 2018, 140, 5798−
5804. (e) Wu, M.; Miao, C.-X.; Wang, S.; Hu, X.; Xia, C.; Ku
̈
hn, F. E.;
(8) For recent remarkable examples using Mn: (a) Paradine, S. M.;
Griffin, J. R.; Zhao, J.; Petronico, A. L.; Miller, S. M.; White, M. C. A
Manganese Catalyst for Highly Reactive yet Chemoselective Intra-
molecular C(sp3)−H Amination. Nat. Chem. 2015, 7, 987−994.
(b) Clark, J. R.; Feng, K.; Sookezian, A.; White, M. C. Manganese-
Catalysed Benzylic C(sp3)−H Amination for Late-Stage Functional-
ization. Nat. Chem. 2018, 10, 583−591. (c) Yu, X.-Q.; Huang, J.-S.;
Zhou, X.-G.; Che, C.-M. Amidation of Saturated C−H Bonds
Catalyzed by Electron-Deficient Ruthenium and Manganese Porphyr-
ins. A Highly Catalytic Nitrogen Atom Transfer Process. Org. Lett.
2000, 2, 2233−2236.
Sun, W. Chiral Bioinspired Non-Heme Iron Complexes for
Enantioselective Epoxidation of α,β-Unsaturated Ketones. Adv.
Synth. Catal. 2011, 353, 3014−3022. (f) Oloo, W. N.; Que, L., Jr.
Bioinspired Nonheme Iron Catalysts for C−H and C=C Bond
Oxidation: Insights into the Nature of the Metal-Based Oxidants. Acc.
́
Chem. Res. 2015, 48, 2612−2621. (g) Olivo, G.; Cusso, O.; Borrell,
M.; Costas, M. Oxidation of Alkane and Alkene Moieties with
Biologically Inspired Nonheme Iron Catalysts and Hydrogen
Peroxide: from Free Radicals to Stereoselective Transformations.
JBIC, J. Biol. Inorg. Chem. 2017, 22, 425−452.
(15) Stoichiometric aromatic amination of iron−aminopyridine
complex was previously reported; see: (a) Jensen, M. P.; Mehn, M. P.;
Que, L., Jr. Intramolecular Aromatic Amination through Iron-
Mediated Nitrene Transfer. Angew. Chem., Int. Ed. 2003, 42, 4357−
4360. (b) For the only catalytic example using Que’s complex in
amination of activated C(sp3)−H bonds, see ref 7g.
(16) Lenze, M.; Martin, E. T.; Rath, N. P.; Bauer, E. B. Iron(II) α-
Aminopyridine Complexes and Their Catalytic Activity in Oxidation
Reactions: A Comparative Study of Activity and Ligand Decom-
position. ChemPlusChem 2013, 78, 101−116.
(9) Selected C−H amination examples using Co: (a) Zhang, L.; Liu,
Y.; Deng, L. Three-Coordinate Cobalt(IV) and Cobalt(V) Imido
Complexes with N-Heterocyclic Carbene Ligation: Synthesis,
Structure, and Their Distinct Reactivity in C−H Bond Amination.
J. Am. Chem. Soc. 2014, 136, 15525−15528. (b) Lu, H.; Jiang, H.;
Wojtas, L.; Zhang, X. P. Selective Intramolecular C−H Amination
through the Metalloradical Activation of Azides: Synthesis of 1,3-
Diamines under Neutral and Nonoxidative Conditions. Angew. Chem.,
Int. Ed. 2010, 49, 10192−10196. Selected examples using Cu:
(c) Aguila, M. J. B.; Badiei, Y. M.; Warren, T. H. Mechanistic Insights
into C−H Amination via Dicopper Nitrenes. J. Am. Chem. Soc. 2013,
135, 9399−9406. (d) Bagchi, V.; Paraskevopoulou, P.; Das, P.; Chi,
L.; Wang, Q.; Choudhury, A.; Mathieson, J. S.; Cronin, L.; Pardue, D.
B.; Cundari, T. R.; Mitrikas, G.; Sanakis, Y.; Stavropoulos, P. A
Versatile Tripodal Cu(I) Reagent for C−N Bond Construction via
Nitrene-Transfer Chemistry: Catalytic Perspectives and Mechanistic
Insights on C−H Aminations/Amidinations and Olefin Aziridina-
tions. J. Am. Chem. Soc. 2014, 136, 11362−11381.
(17) Selected recent examples that showed the enhancement of
reactivity by adding a second ligand: (a) Everson, D. A.; Shrestha, R.;
Weix, D. J. Nickel-Catalyzed Reductive Cross-Coupling of Aryl
Halides with Alkyl Halides. J. Am. Chem. Soc. 2010, 132, 920−921.
(b) Sheng, J.; Ni, H.-Q.; Zhang, H.-R.; Zhang, K.-F.; Wang, Y.-N.;
Wang, X.-S. Nickel-Catalyzed Reductive Cross-Coupling of Aryl
Halides with Monofluoroalkyl Halides for Late-Stage Monofluor-
oalkylation. Angew. Chem., Int. Ed. 2018, 57, 7634−7639.
(18) (a) For previous synthesis of [Fe-1], see: Liu, C.-M.; Gao, H.-
Y.; Zhang, D.-Q.; Zhu, D.-B. Solvothermal In Situ Ligand Synthesis,
Crystal Structure and Fluorescent Properties of a New Heterocyclic
(10) (a) Breslow, R.; Gellman, S. H. Tosylamidation of Cyclohexane
by a Cytochrome P-450 Model. J. Chem. Soc., Chem. Commun. 1982,
E
Org. Lett. XXXX, XXX, XXX−XXX