Page 5 of 6
ACS Catalysis
2018, 10, 5323-5330; (f) Adams, A. M.; Du Bois, J., Organocatalytic C–
Margarida Borrell 0000-0002-5821-7005
Sergio Gil-Caballero 0000-0001-8743-8301
Notes
H hydroxylation with Oxone® enabled by an aqueous fluoroalcohol solvent
system. Chem. Sci. 2014, 5, 656-659; (g) It has been proposed that
hydrogen peroxide forms microdroplets in HFIP; Hollóczki, O.; Berkessel,
A.; Mars, J.; Mezger, M.; Wiebe, A.; Waldvogel, S. R.; Kirchner, B., The
Catalytic Effect of Fluoroalcohol Mixtures Depends on Domain Formation.
ACS Catal. 2017, 7, 1846-1852; (h) For an alternative role of HFIP in
organocatalytic C-H oxidations, forming microdoplets that concentrate
reagents and improve catalyst stability see: Addams, A. M.; Du Bois, J.,
Organocatalytic C–H hydroxylation with Oxone® enabled by an aqueous
fluoroalcohol solvent system. Chem. Sci. 2014, 5, 656-659.
1
2
3
4
5
6
7
8
The authors declare no competing financial interest.
ACKNOWLEDGEMENTS
Support by the Spanish Ministry of Science (PGC2018-101737-
B-I00 to M.C. and PhD grant to M.B. BES-2016-076349), and
Generalitat de Catalunya (ICREA Academia Award to M.C. and
2017 SGR 00264) is acknowledged. We thank Prof. Sergio
Castillón for experimental support in the synthesis of glycosides.
(7) Borrell, M.; Costas, M., Mechanistically Driven Development of an
Iron Catalyst for Selective Syn-Dihydroxylation of Alkenes with Aqueous
Hydrogen Peroxide. J. Am. Chem. Soc. 2017, 139, 12821-12829.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(8)
Milan, M.; Bietti, M.; Costas, M., Highly Enantioselective
Oxidation of Nonactivated Aliphatic C-H Bonds with Hydrogen Peroxide
Catalyzed by Manganese Complexes. Acs Cent. Sci. 2017, 3, 196-204.
(9) We thank an anonymous reviewer for suggesting this experiment.
(10) Abraham, M. H.; Grellier, P. L.; Prior, D. V.; Duce, P. P.; Morris,
J. J.; Taylor, P. J., Hydrogen bonding. Part 7. A scale of solute hydrogen-
bond acidity based on log K values for complexation in tetrachloromethane.
J. Chem. Soc. Perkin Trans. 2 1989, 699-711.
(11) Berkessel, A.; Adrio, J. A., Dramatic Acceleration of Olefin
Epoxidation in Fluorinated Alcohols:ꢀ Activation of Hydrogen Peroxide by
Multiple H-Bond Networks. J. Am. Chem. Soc. 2006, 128, 13412-13420.
REFERENCES
(1) (a)
Plietker, B.; Niggemann, M., The RuO4-catalysed
dihydroxylation, ketohydroxylation and mono oxidation—novel oxidation
reactions for the synthesis of diols and α-hydroxy ketones. Org. Biomol.
Chem. 2004, 2, 2403-2407; (b)
Ketohydroxylation. Part 1. Development, Scope, and Limitation. J. Org.
Chem. 2004, 69, 8287-8296; (c) Maki, T.; Iikawa, S.; Mogami, G.;
Harasawa, H.; Matsumura, Y.; Onomura, O., Efficient Oxidation of 1,2-
Diols into α-Hydroxyketones Catalyzed by Organotin Compounds. Chem.
Plietker, B., The RuO4-Catalyzed
(12)
Fukuzumi, S., Unified Mechanism of Oxygen Atom Transfer and Hydrogen
Atom Transfer Reactions with Triflic Acid-Bound Nonheme
Lee, Y.-M.; Kim, S.; Ohkubo, K.; Kim, K.-H.; Nam, W.;
Eur. J. 2009, 15, 5364-5370; (d)
Painter, R. M.; Pearson, D. M.;
a
Waymouth, R. M., Selective Catalytic Oxidation of Glycerol to
Dihydroxyacetone. Angew. Chem. Int. Ed. 2010, 49, 9456-9459; (e)
Chung, K.; Banik, S. M.; De Crisci, A. G.; Pearson, D. M.; Blake, T. R.;
Olsson, J. V.; Ingram, A. J.; Zare, R. N.; Waymouth, R. M., Chemoselective
Pd-Catalyzed Oxidation of Polyols: Synthetic Scope and Mechanistic
Studies. J. Am. Chem. Soc. 2013, 135, 7593-7602; (f) Hung, K.; Condakes,
M. L.; Morikawa, T.; Maimone, T. J., Oxidative Entry into the Illicium
Sesquiterpenes: Enantiospecific Synthesis of (+)-Pseudoanisatin. J. Am.
Chem. Soc. 2016, 138, 16616-16619; (g) Hill, C. K.; Hartwig, J. F., Site-
selective oxidation, amination and epimerization reactions of complex
polyols enabled by transfer hydrogenation. Nat. Chem. 2017, 9, 1213; (h)
Hung, K.; Condakes, M. L.; Novaes, L. F. T.; Harwood, S. J.; Morikawa,
T.; Yang, Z.; Maimone, T. J., Development of a Terpene Feedstock-Based
Oxidative Synthetic Approach to the Illicium Sesquiterpenes. J. Am. Chem.
Soc. 2019, 141, 3083-3099.
(2) Bietti, M., Activation and Deactivation Strategies Promoted by
Medium Effects for Selective Aliphatic C−H Bond Functionalization.
Angew. Chem. Int. Ed. 2018, 57, 16618-16637.
(3) Spannring, P.; Bruijnincx, P. C. A.; Weckhuysen, B. M.; Gebbink,
R. J. M. K., Transition metal-catalyzed oxidative double bond cleavage of
simple and bio-derived alkenes and unsaturated fatty acids. Catal. Sci.
Technol. 2014, 4, 2182-2209.
(4) (a) Serrano-Plana, J.; Oloo, W. N.; Acosta-Rueda, L.; Meier, K. K.;
Verdejo, B.; García-España, E.; Basallote, M. G.; Münck, E.; Que, L.;
Company, A.; Costas, M., Trapping a Highly Reactive Nonheme Iron
Intermediate That Oxygenates Strong C—H Bonds with Stereoretention. J.
Am. Chem. Soc. 2015, 137, 15833-15842; (b) Ottenbacher, R. V.; Talsi, E.
P.; Bryliakov, K. P., Mechanism of Selective C–H Hydroxylation Mediated
by Manganese Aminopyridine Enzyme Models. ACS Catal. 2015, 5, 39-44.
(5) (a) Sheldon, R. A.; Arends, I. W. C. E.; ten Brink, G.-J.; Dijksman,
A., Green, Catalytic Oxidations of Alcohols. Acc. Chem. Res. 2002, 35,
774-781; (b) Ryland, B. L.; Stahl, S. S., Practical Aerobic Oxidations of
Alcohols and Amines with Homogeneous Copper/TEMPO and Related
Catalyst Systems. Angew. Chem. Int. Ed. 2014, 53, 8824-8838.
(6) (a) P. Roberts, B., Polarity-reversal catalysis of hydrogen-atom
abstraction reactions: concepts and applications in organic chemistry.
Chem. Soc. Rev. 1999, 28, 25-35; (b) Wang, D.; Shuler, W. G.; Pierce, C.
J.; Hilinski, M. K., An Iminium Salt Organocatalyst for Selective Aliphatic
C–H Hydroxylation. Org. Lett. 2016, 18, 3826-3829; (c) Gaster, E.;
Kozuch, S.; Pappo, D., Selective Aerobic Oxidation of Methylarenes to
Benzaldehydes Catalyzed by N-Hydroxyphthalimide and Cobalt(II)
Acetate in Hexafluoropropan-2-ol. Angew. Chem. Int. Ed. 2017, 56, 5912-
5915; (d) Dantignana, V.; Milan, M.; Cussó, O.; Company, A.; Bietti, M.;
Costas, M., Chemoselective Aliphatic C–H Bond Oxidation Enabled by
Polarity Reversal. Acs Cent. Sci. 2017, 3, 1350-1358; (e) Ottenbacher, R.
V.; Talsi, E. P.; Rybalova, T. V.; Bryliakov, K. P., Enantioselective
Benzylic Hydroxylation of Arylalkanes with H2O2 in Fluorinated Alcohols
in the Presence of Chiral Mn Aminopyridine Complexes. ChemCamChem
Manganese(IV)–Oxo Complex via Outer-Sphere Electron Transfer. J. Am.
Chem. Soc. 2019, 141, 2614-2622.
(13) (a) Ottenbacher, R. V.; Samsonenko, D. G.; Talsi, E. P.; Bryliakov,
K. P., Highly Efficient, Regioselective, and Stereospecific Oxidation of
Aliphatic C-H Groups with H2O2, Catalyzed by Aminopyridine
Manganese Complexes. Org. Lett. 2012, 14, 4310–4313; (b) O.Cussó;
Garcia-Bosch, I.; Ribas, X.; Lloret-Fillol, J.; Costas, M., Asymmetric
Epoxidation with H2O2 by Manipulating the Electronic Properties of Non-
heme Iron Catalysts. J. Am. Chem. Soc. 2013, 135, 14871-14878; (c)
Cussó, O.; Garcia-Bosch, I.; Font, D.; Ribas, X.; Lloret-Fillol, J.; Costas,
M., Highly Stereoselective Epoxidation with H2O2 Catalyzed by Electron-
Rich Aminopyridine Manganese Catalysts. Org. Lett. 2013, 15, 6158-6161;
(d) Font, D.; Canta, M.; Milan, M.; Cusso, O.; Ribas, X.; Gebbink, R. J.
M. K.; Costas, M., Readily Accessible Bulky Iron Catalysts exhibiting Site
Selectivity in the Oxidation of Steroidal Substrates. Angew. Chem. Int. Ed.
2016, 55, 5776-5779; (e) Milan, M.; Carboni, G.; Salamone, M.; Costas,
M.; Bietti, M., Tuning Selectivity in Aliphatic C–H Bond Oxidation of N-
Alkylamides and Phthalimides Catalyzed by Manganese Complexes. ACS
Catal. 2017, 7, 5903-5911.
(14) (a) Chen, M. S.; White, M. C., A predictably selective aliphatic C-
H oxidation reaction for complex molecule synthesis. Science 2007, 318,
783-7; (b) White, M. C.; Zhao, J., Aliphatic C–H Oxidations for Late-
Stage Functionalization. J. Am. Chem. Soc. 2018, 140, 13988-14009.
(15) GC yields were determined in order to have an accurate ratio
between products.
(16) Milan, M.; Bietti, M.; Costas, M., Enantioselective aliphatic C-H
bond oxidation catalyzed by bioinspired complexes. Chem. Commun. 2018,
54, 9559-9570.
(17) (a)
Tsuda, Y.; Hanajima, M.; Matsuhira, N.; Okuno, Y.;
Kanemitsu, K., Regioselective Mono-oxidation of Non-protected
Carbohydrates by Brominolysis of the Tin Intermediates. Chem. Pharm.
Bull. 1989, 37, 2344-2350; (b) Freimund, S.; Huwig, A.; Giffhorn, F.;
Köpper, S., Rare Keto-Aldoses from Enzymatic Oxidation: Substrates and
Oxidation Products of Pyranose 2-Oxidase. Chem. Eur. J. 1998, 4, 2442-
2455; (c) Perlin, A. S., Glycol-Cleavage Oxidation. In Adv. Carbohydr.
Chem. Biochem., Horton, D., Ed. Academic Press: 2006; Vol. 60, pp 183-
250; (d) Jäger, M.; Hartmann, M.; deꢁVries, J. G.; Minnaard, A. J.,
Catalytic Regioselective Oxidation of Glycosides. Angew. Chem. Int. Ed.
2013, 52, 7809-7812; (e) Muramatsu, W., Catalytic and Regioselective
Oxidation of Carbohydrates To Synthesize Keto-Sugars under Mild
Conditions. Org. Lett. 2014, 16, 4846-4849; (f) Jäger, M.; Minnaard, A.
J., Regioselective modification of unprotected glycosides. Chem. Commun.
2016, 52, 656-664; (g) Shang, W.; He, B.; Niu, D., Ligand-controlled,
transition-metal catalyzed site-selective modification of glycosides.
Carbohydr. Res. 2019, 474, 16-33.
(18)
Alexander, C.; Rietschel, E. T., Invited review: Bacterial
ACS Paragon Plus Environment