Undirected, homogeneous C-H bond functionalization: Challenges and opportunities

ACS Central Science

Volumn 2, Issue 5, 2016, Pages 281-292

  Hartwig, John F ^a,b   Larsen, Matthew A ^a,b  

^a UNIVERSITY OF CALIFORNIA   (United States)

^b LAWRENCE BERKELEY NATIONAL LABORATORY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ASSOCIATION REACTIONS; MOLECULES;

C-H BOND CLEAVAGE; C-H BOND FUNCTIONALIZATION; C-H FUNCTIONALIZATION; COMPLEX MOLECULES; FUNCTIONALIZATION REACTIONS; FUNCTIONALIZATIONS; NONCOVALENT ASSOCIATION; ORGANIC MOLECULES;

COORDINATION REACTIONS;

EID: 84990836654     PISSN: 23747943     EISSN: 23747951     Source Type: Journal    
DOI: 10.1021/acscentsci.6b00032     Document Type: Article

References (145)

1. Godula, K.; Sames, D. C-H Bond Functionalization in Complex Organic Synthesis. Science 2006, 312, 67-72.
2. Wencel-Delord, J.; Glorius, F. C-H bond activation enables the rapid construction and late-stage diversification of functional molecules. Nat. Chem. 2013, 5, 369-375.
3. Labinger, J. A.; Bercaw, J. E. Understanding and exploiting C-H bond activation. Nature 2002, 417, 507-514.
4. White, M. C. Adding Aliphatic C-H Bond Oxidations to Synthesis. Science 2012, 335, 807-809.
5. Lyons, T. W.; Sanford, M. S. Palladium-Catalyzed Ligand- Directed C-H Functionalization Reactions. Chem. Rev. 2010, 110, 1147-1169.
6. Jun, C.-H.; Hong, J.-B.; Kim, Y.-H.; Chung, K.-Y. The catalytic alkylation of aromatic imines by Wilkinson's complex: the domino reaction of hydroacylation and ortho-alkylation. Angew. Chem., Int. Ed. 2000, 39, 3440-3442.
7. Zaitsev, V. G.; Shabashov, D.; Daugulis, A. Highly regioselective arylation of sp3 C-H bonds catalyzed by palladium acetate. J. Am. Chem. Soc. 2005, 127, 13154-13155.
8. Tang, R. Y.; Li, G.; Yu, J. Q. Conformation-induced remote meta- C-H activation of amines. Nature 2014, 507, 215-220.
9. Wan, L.; Dastbaravardeh, N.; Li, G.; Yu, J. Q. Cross-Coupling of Remote meta-C-H Bonds Directed by a U-Shaped Template. J. Am. Chem. Soc. 2013, 135, 18056-18059.
10. Leow, D.; Li, G.; Mei, T. S.; Yu, J. Q. Activation of remote meta- C-H bonds assisted by an end-on template. Nature 2012, 486, 518-522.
11. Zhang, M.; Zhang, Y.; Jie, X.; Zhao, H.; Li, G.; Su, W. Recent advances in directed C-H functionalizations using monodentate nitrogen-based directing groups. Org. Chem. Front. 2014, 1, 843-895.
12. Kleiman, J. P.; Dubeck, M. The Preparation of Cyclopentadienyl [o-(Phenylazo)Phenyl]Nickel. J. Am. Chem. Soc. 1963, 85, 1544-1545.
13. Cope, A. C.; Siekman, R. W. Formation of Covalent Bonds from Platinum or Palladium to Carbon by Direct Substitution. J. Am. Chem. Soc. 1965, 87, 3272-3273.
14. Fahey, D. R. The coordination-catalyzed ortho-halogenation of azobenzene. J. Organomet. Chem. 1971, 27, 283-292.
15. Kodama, H.; Katsuhira, T.; Nishida, T.; Hino, T.; Tsubata, K. Process for the preparation of 2-halobenzoic acids. In PCT/JP2001/003707; Nihon Nohyaku Co Ltd: Japan, 2001.
16. Engle, K. M.; Mei, T.-S.; Wasa, M.; Yu, J.-Q. Weak Coordination as a Powerful Means for Developing Broadly Useful C-H Functionalization Reactions. Acc. Chem. Res. 2012, 45, 788-802.
17. DiRocco, D. A.; Dykstra, K.; Krska, S.; Vachal, P.; Conway, D. V.; Tudge, M. Late-Stage Functionalization of Biologically Active Heterocycles Through Photoredox Catalysis. Angew. Chem., Int. Ed. 2014, 53, 4802-4806.
18. In honor of Derek Barton, Jack Roberts conceived the "Barton Challenge" (see ref 19), which was to make adipic acid from oxidation of n-hexane in 85% yield. Although the use of n-hexane would unlikely compete with the route to adipic acid starting from cyclohexane, the direct functionalization of the terminal C-H bonds of other length alkanes or renewable, long-chain materials could be a valuable route to monomers.
19. Wilson, E. Barton Challenge: Adipic acid from n-hexane. Chem. Eng. News 1999, 77 (1), 24.
20. Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Selective Intermolecular Carbon-Hydrogen Bond Activation by Synthetic Metal Complexes in Homogeneous Solution. Acc. Chem. Res. 1995, 28, 154-162.
21. Newhouse, T.; Baran, P. S. If C-H Bonds Could Talk: Selective C-H Bond Oxidation. Angew. Chem., Int. Ed. 2011, 50, 3362-3374.
22. Falbe, J.; Bahrmann, H.; Lipps, W.; Mayer, D.; Frey, G. D.: Alcohols, Aliphatic. In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000.
23. Werle, P.; Morawietz, M.; Lundmark, S.; Sörensen, K.; Karvinen, E.; Lehtonen, J.: Alcohols, Polyhydric. In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000.
24. Roose, P.; Eller, K.; Henkes, E.; Rossbacher, R.; Höke, H.: Section 8.1 of Amines, Aliphatic. In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000.
25. Smith, M. B.; March, J. Aromatic Substitution, Electrophilic. In March's Advanced Organic Chemistry, 6th ed.; John Wiley and Sons: New York, 2007; Chapter 11, pp 853-933.
26. Beak, P.; Snieckus, V. Directed lithiation of aromatic tertiary amides: an evolving synthetic methodology for polysubstituted aromatics. Acc. Chem. Res. 1982, 15, 306-312.
27. Whisler, M. C.; MacNeil, S.; Snieckus, V.; Beak, P. Beyond thermodynamic acidity: A perspective on the complex-induced proximity effect (CIPE) in deprotonation reactions. Angew. Chem., Int. Ed. 2004, 43, 2206-2225.
28. Bordwell, F. G. Equilibrium Acidities in Dimethyl Sulfoxide Solution. Acc. Chem. Res. 1988, 21, 456-463.
29. Mayr, H.; Ofial, A. R. The reactivity-selectivity principle: an imperishable myth in organic chemistry. Angew. Chem., Int. Ed. 2006, 45, 1844-1854.
30. Jones, W. D.; Hessell, E. T. Photolysis of Tp'Rh(CNneopentyl)( ν2-PhN:C:N-neopentyl) in alkanes and arenes: kinetic and thermodynamic selectivity of [Tp'Rh(CN-neopentyl)] for various types of carbon-hydrogen bonds. J. Am. Chem. Soc. 1993, 115, 554-562.
31. Harvey, J. N. Electronic Effects on the Stability of Isomeric Alkyl Transition Metal Compounds. Organometallics 2001, 20, 4887-4895.
32. Reger, D. L.; Ding, Y.; Garza, D. G.; Lebioda, L. Influence of the size of the phosphine ligand on primary-secondary alkyl isomerization equilibria with (Me2NCS2)Pt(PR3) (alkyl) complexes. J. Organomet. Chem. 1993, 452, 263-270.
33. Reger, D. L.; Garza, D. G.; Lebioda, L. Isomerization of the alkyl ligand in (Me2NCS2)Pd(PR3) (alkyl) complexes. Influences of heteroatom substituents in the alkyl group on the alkyl isomerization equilibria and stability of alkylmetal complexes. Organometallics 1992, 11, 4285-4292.
34. Schmidt, V. A.; Quinn, R. K.; Brusoe, A. T.; Alexanian, E. J. Site- Selective Aliphatic C-H Bromination Using N-Bromoamides and Visible Light. J. Am. Chem. Soc. 2014, 136, 14389-14392.
35. Liskey, C. W.; Hartwig, J. F. Iridium-Catalyzed Borylation of Secondary C-H Bonds in Cyclic Ethers. J. Am. Chem. Soc. 2012, 134, 12422-12425.
36. Murahashi, S. I.; Komiya, N.; Terai, H.; Nakae, T. Aerobic ruthenium-catalyzed oxidative cyanation of tertiary amines with sodium cyanide. J. Am. Chem. Soc. 2003, 125, 15312-15313.
37. Luecke, H. F.; Arndtsen, B. A.; Burger, P.; Bergman, R. G. Synthesis of Fischer Carbene Complexes of Iridium by C-H Bond Activation of Methyl and Cyclic Ethers: Evidence for Reversible α- Hydrogen Migration. J. Am. Chem. Soc. 1996, 118, 2517-2518.
38. Li, Z.; Bohle, D. S.; Li, C.-J. Cu-catalyzed cross-dehydrogenative coupling: A versatile strategy for C-C bond formations via the oxidative activation of sp3 C-H bonds. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 8928-8933.
39. Musser, M. T.: Cyclohexanol and Cyclohexanone. In Ullmanns Encyclopedia of Industrial Chemistry (Online); John Wiley and Sons: New York, 2005. http://www.mrw.interscience.wiley.com/ueic/articles/a08-217/sect3-fs.html.
40. Goldman, A. S.; Renkema, K. B.; Czerw, M.; Krogh-Jespersen, K. Alkane Transfer-Dehydrogenation Catalyzed by a Pincer-Ligated Iridium Complex. In Activation and Functionalization of C-H Bonds; Goldberg, K. I., Goldman, A. S., Eds.; American Chemical Society: Washington, DC, 2004; Vol. 885; pp 198-215.
41. Hartwig, J. F. Dehydrogenation. In Organotransition Metal Chemistry; University Science Books: Sausalito, CA, 2010; section 18.5, pp 839-846.
42. Choi, J.; MacArthur, A. H. R.; Brookhart, M.; Goldman, A. S. Dehydrogenation and Related Reactions Catalyzed by Iridium Pincer Complexes. Chem. Rev. 2011, 111, 1761-1779.
43. Davies, H. M. L.; Beckwith, R. E. J. Catalytic Enantioselective C-H Activation by Means of Metal-Carbenoid-Induced C-H Insertion. Chem. Rev. 2003, 103, 2861-2904.
44. Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F. C-H Activation for the Construction of C-B Bonds. Chem. Rev. 2010, 110, 890-931.
45. Cheng, C.; Hartwig, J. F. Catalytic Silylation of Unactivated C-H Bonds. Chem. Rev. 2015, 115, 8946-8975.
46. Hartwig, J. F. Borylation and Silylation of C-H Bonds: A Platform for Diverse C-H Bond Functionalizations. Acc. Chem. Res. 2012, 45, 864-873.
47. Chen, H.; Schlecht, S.; Semple, T. C.; Hartwig, J. F. Thermal, Catalytic, Regiospecific Functionalization of Alkanes. Science 2000, 287, 1995-1997.
48. Larsen, M. A.; Wilson, C. V.; Hartwig, J. F. Iridium-Catalyzed Borylation of Primary Benzylic C-H Bonds without a Directing Group: Scope, Mechanism, and Origins of Selectivity. J. Am. Chem. Soc. 2015, 137, 8633-8643.
49. Li, Q.; Liskey, C. W.; Hartwig, J. F. Regioselective Borylation of the C-H Bonds in Alkylamines and Alkyl Ethers. Observation and Origin of High Reactivity of Primary C-H Bonds Beta to Nitrogen and Oxygen. J. Am. Chem. Soc. 2014, 136, 8755-8765.
50. Murphy, J. M.; Lawrence, J. D.; Kawamura, K.; Incarvito, C.; Hartwig, J. F. Ruthenium-Catalyzed Regiospecific Borylation of Methyl C-H Bonds. J. Am. Chem. Soc. 2006, 128, 13684.
51. Baudry, D.; Ephritikhine, M.; Felkin, H.; Zakrzewski, J. The Selective Conversion of Normal-Pentane Into Pent-1-Ene Via Trihydrido(Trans-Penta-1, 3-Diene)Bis(Triarylphosphine)Rhenium. J. Chem. Soc., Chem. Commun. 1982, 1235-1236.
52. Liu, F. C.; Goldman, A. S. Efficient thermochemical alkane dehydrogenation and isomerization catalyzed by an iridium pincer complex. Chem. Commun. 1999, 655-656.
53. Kumar, A.; Zhou, T.; Emge, T. J.; Mironov, O.; Saxton, R. J.; Krogh-Jespersen, K.; Goldman, A. S. Dehydrogenation of n-Alkanes by Solid-Phase Molecular Pincer-Iridium Catalysts. High Yields of alpha-Olefin Product. J. Am. Chem. Soc. 2015, 137, 9894-9911.
54. Chowdhury, A. D.; Weding, N.; Julis, J.; Franke, R.; Jackstell, R.; Beller, M. Towards a Practical Development of Light-Driven Acceptorless Alkane Dehydrogenation. Angew. Chem. Int. Ed. 2014, 53, 6477-6481.
55. Goldman, A. S.; Roy, A. H.; Huang, Z.; Ahuja, R.; Schinski, W.; Brookhart, M. Catalytic Alkane Metathesis by Tandem Alkane Dehydrogenation-Olefin Metathesis. Science 2006, 312, 257-261.
56. Jia, X.; Huang, Z. Conversion of alkanes to linear alkylsilanes using an iridium-iron-catalysed tandem dehydrogenation-isomerization- hydrosilylation. Nat. Chem. 2016, 8, 157-161.
57. Shilov, A. E.; Shteinman, A. A. Activation of saturated hydrocarbons by metal complexes in solution. Coord. Chem. Rev. 1977, 24, 97-143.
58. Lin, M.; Shen, C.; Garcia-Zayas, E. A.; Sen, A. Catalytic Shilov Chemistry: Platinum Chloride-Catalyzed Oxidation of Terminal Methyl Groups by Dioxygen. J. Am. Chem. Soc. 2001, 123, 1000-1001.
59. Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Satoh, T.; Fujii, H. Platinum Catalysts for the High-Yield Oxidation of Methane to a Methanol Derivative. Science 1998, 280, 560-564.
60. Chen, M. S.; White, M. C. Combined Effects on Selectivity in Fe-Catalyzed Methylene Oxidation. Science 2010, 327, 566-571.
61. Ohara, T.; Sato, T.; Shimizu, N.; Prescher, G.; Schwind, H.; Weiberg, O.; Marten, K.; Greim, H.: Acrylic Acid and Derivatives. In Ullmann's Encyclopedia of Industrial Chemistry; Wiley-VCH Verlag GmbH & Co. KGaA: 2000.
62. Adam, W.; Curci, R.; Edwards, J. O. Dioxiranes: a new class of powerful oxidants. Acc. Chem. Res. 1989, 22, 205-211.
63. Brodsky, B. H.; Du Bois, J. Oxaziridine-mediated catalytic hydroxylation of unactivated 3° C-H bonds using hydrogen peroxide. J. Am. Chem. Soc. 2005, 127, 15391-15393.
64. Annese, C.; D'Accolti, L.; Fusco, C.; Curci, R. Selective Hydroxylation of Methane by Dioxiranes under Mild Conditions. Org. Lett. 2011, 13, 2142-2144.
65. Bovicelli, P.; Lupattelli, P.; Mincione, E.; Prencipe, T.; Curci, R. Oxidation of natural targets by dioxiranes. 2. Direct hydroxylation at the side chain C-25 of cholestane derivatives and of vitamin D3 Windaus-Grundmann ketone. J. Org. Chem. 1992, 57, 5052-5054.
66. Voigt, B.; Porzel, A.; Golsch, D.; Adam, W.; Adam, G. Regioselective oxyfunctionalization of brassinosteroids by methyl- (trifluoromethyl)dioxirane: Synthesis of 25-hydroxy-brassinolide and 25-hydroxy-24-epibrassinolide by direct C-H insertion. Tetrahedron 1996, 52, 10653-10658.
67. Seto, H.; Fujioka, S.; Koshino, H.; Yoshida, S.; Tsubuki, M.; Honda, T. Synthesis and biological evaluation of extra-hydroxylated brassinolide analogs. Tetrahedron 1999, 55, 8341-8352.
68. Hinman, A.; Du Bois, J. A stereoselective synthesis of (-)-tetrodotoxin. J. Am. Chem. Soc. 2003, 125, 11510-11511.
69. Roizen, J. L.; Zalatan, D. N.; Du Bois, J. Selective Intermolecular Amination of C-H Bonds at Tertiary Carbon Centers. Angew. Chem., Int. Ed. 2013, 52, 11343-11346.
70. Sharma, A.; Hartwig, J. F. Metal-catalysed azidation of tertiary C-H bonds suitable for late-stage functionalization. Nature 2015, 517, 600-604.
71. Liu, W.; Groves, J. T. Manganese Catalyzed C-H Halogenation. Acc. Chem. Res. 2015, 48, 1727-1735.
72. Liu, W.; Groves, J. T. Manganese Porphyrins Catalyze Selective C-H Bond Halogenations. J. Am. Chem. Soc. 2010, 132, 12847-12849.
73. Liu, W.; Huang, X.; Cheng, M.-J.; Nielsen, R. J.; Goddard, W. A.; Groves, J. T. Oxidative Aliphatic C-H Fluorination with Fluoride Ion Catalyzed by a Manganese Porphyrin. Science 2012, 337, 1322-1325.
74. Huang, X.; Liu, W.; Ren, H.; Neelamegam, R.; Hooker, J. M.; Groves, J. T. Late Stage Benzylic C-H Fluorination with [18F]- Fluoride for PET Imaging. J. Am. Chem. Soc. 2014, 136, 6842-6845.
75. For a system that catalyzes azidation of C-H bonds by a related mechanism, see: Huang, X.; Bergsten, T. M.; Groves, J. T. Manganese- Catalyzed Late-Stage Aliphatic C-H Azidation. J. Am. Chem. Soc. 2015, 137, 5300-5303.
76. Olah, G. A.; Wu, A. H.; Farooq, O. Synthetic methods and reactions. 137. Ionic chlorination (bromination) of alkanes and cycloalkanes with methylene chloride (bromide)/antimony pentafluoride. J. Org. Chem. 1989, 54, 1463-1465.
77. Davies, H. M. L.; Manning, J. R. Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion. Nature 2008, 451, 417-424.
78. Hansen, J.; Autschbach, J.; Davies, H. M. L. Computational Study on the Selectivity of Donor/Acceptor-Substituted Rhodium Carbenoids. J. Org. Chem. 2009, 74, 6555-6563.
79. Davies, H. M. L.; Hansen, T.; Churchill, M. R. Catalytic asymmetric C-H activation of alkanes and tetrahydrofuran. J. Am. Chem. Soc. 2000, 122, 3063-3070.
80. Davies, H. M. L.; Hansen, T.; Hopper, D. W.; Panaro, S. A. Highly regio-, diastereo-, and enantioselective C-H insertions of methyl aryldiazoacetates into cyclic N-BOC-protected amines. Asymmetric synthesis of novel C-2-symmetric amines and threomethylphenidate. J. Am. Chem. Soc. 1999, 121, 6509-6510.
81. Davies, H. M. L.; Antoulinakis, E. G.; Hansen, T. Catalytic Asymmetric Synthesis of Syn-Aldol Products from Intermolecular C-H Insertions between Allyl Silyl Ethers and Methyl Aryldiazoacetates. Org. Lett. 1999, 1, 383-386.
82. Qin, C.; Davies, H. M. L. Role of Sterically Demanding Chiral Dirhodium Catalysts in Site-Selective C-H Functionalization of Activated Primary C-H Bonds. J. Am. Chem. Soc. 2014, 136, 9792-9796.
83. He, J.; Hamann, L. G.; Davies, H. M. L.; Beckwith, R. E. J. Latestage C-H functionalization of complex alkaloids and drug molecules via intermolecular rhodium-carbenoid insertion. Nat. Commun. 2015, 6, 5943.
84. Davies, H. M. L.; Stafford, D. G.; Hansen, T. Catalytic Asymmetric Synthesis of Diarylacetates and 4, 4-Diarylbutanoates. A Formal Asymmetric Synthesis of (+)-Sertraline. Org. Lett. 1999, 1, 233-236.
85. Davies, H. M. L. Catalytic asymmetric C-H activation of sp3 hybridized C-H bonds by means of carbenoid C-H insertions: applications in organic synthesis. J. Mol. Catal. A: Chem. 2002, 189, 125-135.
86. Cane, D. E.; Thomas, P. J. Synthesis of (dl)-pentalenolactones E and F. J. Am. Chem. Soc. 1984, 106, 5295-5303.
87. Taber, D. F.; Schuchardt, J. L. Intramolecular carbon-hydrogen insertion: synthesis of (+)-pentalenolactone E methyl ester. J. Am. Chem. Soc. 1985, 107, 5289-5290.
88. Davies, H. M. L.; Jin, Q. Intermolecular C-H activation at benzylic positions: synthesis of (+)-imperanene and (-)-α-conidendrin. Tetrahedron: Asymmetry 2003, 14, 941-949.
89. Cheng, C.; Hartwig, J. F. Iridium-Catalyzed Silylation of Aryl C-H Bonds. J. Am. Chem. Soc. 2015, 137, 592-595.
90. Larsen, M. A.; Hartwig, J. F. Iridium-Catalyzed C-H Borylation of Heteroarenes: Scope, Regioselectivity, Application to Late-Stage Functionalization, and Mechanism. J. Am. Chem. Soc. 2014, 136, 4287-4299.
91. Hartwig, J. F. Regioselectivity of the borylation of alkanes and arenes. Chem. Soc. Rev. 2011, 40, 1992-2002.
92. Cheng, C.; Hartwig, J. F. Rhodium-Catalyzed Intermolecular CH Silylation of Arenes with High Steric Regiocontrol. Science 2014, 343, 853-857.
93. Feng, Y.; Holte, D.; Zoller, J.; Umemiya, S.; Simke, L. R.; Baran, P. S. Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C-H Borylation. J. Am. Chem. Soc. 2015, 137, 10160-10163.
94. Campeau, L.-C.; Parisien, M.; Jean, A.; Fagnou, K. Catalytic Direct Arylation with Aryl Chlorides, Bromides, and Iodides: Intramolecular Studies Leading to New Intermolecular Reactions. J. Am. Chem. Soc. 2006, 128, 581-590.
95. Lapointe, D.; Markiewicz, T.; Whipp, C. J.; Toderian, A.; Fagnou, K. Predictable and Site-Selective Functionalization of Poly(hetero)arene Compounds by Palladium Catalysis. J. Org. Chem. 2011, 76, 749-759.
96. Vanchura, B. A., II; Preshlock, S. M.; Roosen, P. C.; Kallepalli, V. A.; Staples, R. J.; Maleczka, R. E., Jr.; Singleton, D. A.; Smith, M. R., III Electronic effects in iridium C-H borylations: insights from unencumbered substrates and variation of boryl ligand substituents. Chem. Commun. 2010, 46, 7724-7726.
97. Takagi, J.; Sato, K.; Hartwig, J. F.; Ishiyama, T.; Miyaura, N. Iridium-catalyzed C-H coupling reaction of heteroaromatic compounds with bis(pinacolato)diboron: regioselective synthesis of heteroarylboronates. Tetrahedron Lett. 2002, 43, 5649-5651.
98. Beck, E. M.; Hatley, R.; Gaunt, M. J. Synthesis of rhazinicine by a metal-catalyzed C-H bond functionalization strategy. Angew. Chem., Int. Ed. 2008, 47, 3004-3007.
99. Kallepalli, V. A.; Shi, F.; Paul, S.; Onyeozili, E. N.; Maleczka, R. E.; Smith, M. R. Boc Groups as Protectors and Directors for Ir-Catalyzed C-H Borylation of Heterocycles. J. Org. Chem. 2009, 74, 9199-9201.
100. Preshlock, S. M.; Plattner, D. L.; Maligres, P. E.; Krska, S. W.; Maleczka, R. E.; Smith, M. R. A Traceless Directing Group for C-H Borylation. Angew. Chem., Int. Ed. 2013, 52, 12915-12919.
101. Campeau, L.-C.; Stuart, D. R.; Leclerc, J.-P.; Bertrand-Laperle, M.; Villemure, E.; Sun, H.-Y.; Lasserre, S.; Guimond, N.; Lecavallier, M.; Fagnou, K. Palladium-Catalyzed Direct Arylation of Azine and Azole N-Oxides: Reaction Development, Scope and Applications in Synthesis. J. Am. Chem. Soc. 2009, 131, 3291-3306.
102. Ishiyama, T.; Takagi, J.; Hartwig, J. F.; Miyaura, N. A Stoichiometric Aromatic C-H Borylation Catalyzed by Iridium(I)/2, 2'-Bipyridine Complexes at Room Temperature. Angew. Chem., Int. Ed. 2002, 41, 3056-3058.
103. Liégault, B.; Lapointe, D.; Caron, L.; Vlassova, A.; Fagnou, K. Establishment of Broadly Applicable Reaction Conditions for the Palladium-Catalyzed Direct Arylation of Heteroatom-Containing Aromatic Compounds. J. Org. Chem. 2009, 74, 1826-1834.
104. Gorelsky, S. I.; Lapointe, D.; Fagnou, K. Analysis of the concerted metalation-deprotonation mechanism in palladium-catalyzed direct arylation across a broad range of aromatic substrates. J. Am. Chem. Soc. 2008, 130, 10848-10849.
105. Larsen, M. A.; Hartwig, J. F. Iridium-Catalyzed C-H Borylation of Heteroarenes: Scope, Regioselectivity, Application to Late-Stage Functionalization, and Mechanism. J. Am. Chem. Soc. 2014, 136, 4287-4299.
106. Cytochrome P450, 4th ed.; Ortiz de Montellano, P. R., Ed.; Springer International Publishing: Basel, 2015.
107. Feig, A. L.; Lippard, S. J. Reactions of Nonheme Iron(II) Centers with Dioxygen in Biology and Chemistry. Chem. Rev. 1994, 94, 759-805.
108. Merkx, M.; Kopp, D. A.; Sazinsky, M. H.; Blazyk, J. L.; Muller, J.; Lippard, S. J. Dioxygen activation and methane hydroxylation by soluble methane monooxygenase: A tale of two irons and three proteins. Angew. Chem., Int. Ed. 2001, 40, 2782-2807.
109. Wallar, B. J.; Lipscomb, J. D. Dioxygen Activation by Enzymes Containing Binuclear Non-Heme Iron Clusters. Chem. Rev. 1996, 96, 2625-2657.
110. Mitchell, K. H.; Rogge, C. E.; Gierahn, T.; Fox, B. G. Insight into the mechanism of aromatic hydroxylation by toluene 4- monooxygenase by use of specifically deuterated toluene and pxylene. Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 3784-3789.
111. Munro, A. W.; Leys, D. G.; McLean, K. J.; Marshall, K. R.; Ost, T. W. B.; Daff, S.; Miles, C. S.; Chapman, S. K.; Lysek, D. A.; Moser, C. C.; Page, C. C.; Dutton, P. L. P450 BM3: the very model of a modern flavocytochrome. Trends Biochem. Sci. 2002, 27, 250-257.
112. Fisher, M. B.; Zheng, Y.-M.; Rettie, A. E. Positional Specificity of Rabbit CYP4B1 for ω-Hydroxylation of Short-Medium Chain Fatty Acids and Hydrocarbons. Biochem. Biophys. Res. Commun. 1998, 248, 352-355.
113. Cahoon, E. B.; Shanklin, J. Substrate dependent mutant complementation to select fatty acid desaturase variants for metabolic engineering of plant seed oils. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 12350-12355.
114. Chau, M.; Jennewein, S.; Walker, K.; Croteau, R. Taxol Biosynthesis: Molecular Cloning and Characterization of a Cytochrome P450 Taxoid 7β-Hydroxylase. Chem. Biol. 2004, 11, 663-672.
115. Ortiz de Montellano, P. R.: Cytochrome P450: Structure, Mechanism, and Biochemistry; Springer International Publishing: 2015.
116. Ichihara, K.; Yamakawa, I.; Kusunose, E.; Kusunose, M. Fatty Acid ω- and (ω-1)-Hydroxylation in Rabbit Intestinal Mucosa Microsomes. J. Biochem. 1979, 86, 139-146.
117. Scheps, D.; Malca, S. H.; Hoffmann, H.; Nestl, B. M.; Hauer, B. Regioselective omega-hydroxylation of medium-chain n-alkanes and primary alcohols by CYP153 enzymes from Mycobacterium marinum and Polaromonas sp strain JS666. Org. Biomol. Chem. 2011, 9, 6727-6733.
118. Landwehr, M.; Hochrein, L.; Otey, C. R.; Kasrayan, A.; Backvall, J. E.; Arnold, F. H. Enantioselective alpha-hydroxylation of 2-arylacetic acid derivatives and buspirone catalyzed by engineered cytochrome P450BM-3. J. Am. Chem. Soc. 2006, 128, 6058-6059.
119. Sawayama, A. M.; Chen, M. M. Y.; Kulanthaivel, P.; Kuo, M.-S.; Hemmerle, H.; Arnold, F. H. A Panel of Cytochrome P450 BM3 Variants to Produce Drug Metabolites and Diversify Lead Compounds. Chem. - Eur. J. 2009, 15, 11723-11729.
120. Kille, S.; Zilly, F. E.; Acevedo, J. P.; Reetz, M. T. Regio- and stereoselectivity of P450-catalysed hydroxylation of steroids controlled by laboratory evolution. Nat. Chem. 2011, 3, 738-743.
121. Breslow, R.; Zhang, X.; Xu, R.; Maletic, M. Merger, R. Selective Catalytic Oxidation of Substrates That Bind to Metalloporphyrin Enzyme Mimics Carrying Two or Four Cyclodextrin Groups and Related Metallosalens. J. Am. Chem. Soc. 1996, 118, 11678-11679.
122. Breslow, R.; Yang, J.; Yan, J. Biomimetic hydroxylation of saturated carbons with artificial cytochrome P-450 enzymes-liberating chemistry from the tyranny of functional groups. Tetrahedron 2002, 58, 653-659.
123. Cook, B. R.; Reinert, T. J.; Suslick, K. S. Shape Selective Alkane Hydroxylation by Metalloporphyrin Catalysts. J. Am. Chem. Soc. 1986, 108, 7281-7286.
124. Das, S.; Incarvito, C. D.; Crabtree, R. H.; Brudvig, G. W. Molecular Recognition in the Selective Oxygenation of Saturated C-H Bonds by a Dimanganese Catalyst. Science 2006, 312, 1941-1943.
125. Kuninobu, Y.; Ida, H.; Nishi, M.; Kanai, M. A meta-selective C-H borylation directed by a secondary interaction between ligand and substrate. Nat. Chem. 2015, 7, 712-717.
126. Ford, A.; Miel, H.; Ring, A.; Slattery, C. N.; Maguire, A. R.; McKervey, M. A. Modern Organic Synthesis with α-Diazocarbonyl Compounds. Chem. Rev. 2015, 115, 9981-10080.
127. Simpson, J. H.; Godfrey, J.; Fox, R.; Kotnis, A.; Kacsur, D.; Hamm, J.; Totelben, M.; Rosso, V.; Mueller, R.; Delaney, E.; Deshpande, R. P. A pilot-scale synthesis of (1R)-trans-2-(2, 3- dihydro-4-benzofuranyl)cyclopropanecarboxylic acid: a practical application of asymmetric cyclopropanation using a styrene as a limiting reagent. Tetrahedron: Asymmetry 2003, 14, 3569-3574.
128. Anthes, R.; Bello, O.; Benoit, S.; Chen, C.-K.; Corbett, E.; Corbett, R. M.; DelMonte, A. J.; Gingras, S.; Livingston, R.; Sausker, J.; Soumeillant, M. Kilogram Synthesis of a Selective Serotonin Reuptake Inhibitor. Org. Process Res. Dev. 2008, 12, 168-177.
129. James, H. S.; Atul, S. K.; Rajendra, P. D.; David, J. K.; Jason, H.; Gus, K.; William, M.; Daniel, D.; Steve, Y. W.: Development of a Multi-Kilogram Procedure To Prepare, Use, and Quench Ethyl Diazoacetate. In Managing Hazardous Reactions and Compounds in Process Chemistry; ACS Symposium Series; American Chemical Society: 2014; Vol. 1181; pp 235-244.
130. Honda Malca, S.; Scheps, D.; Kuhnel, L.; Venegas-Venegas, E.; Seifert, A.; Nestl, B. M.; Hauer, B. Bacterial CYP153A monooxygenases for the synthesis of omega-hydroxylated fatty acids. Chem. Commun. 2012, 48, 5115-5117.
131. Fasan, R.; Meharenna, Y. T.; Snow, C. D.; Poulos, T. L.; Arnold, F. H. Evolutionary History of a Specialized P450 Propane Monooxygenase. J. Mol. Biol. 2008, 383, 1069-1080.
132. Regalado, E. L.; Kozlowski, M. C.; Curto, J. M.; Ritter, T.; Campbell, M. G.; Mazzotti, A. R.; Hamper, B. C.; Spilling, C. D.; Mannino, M. P.; Wan, L.; Yu, J.-Q.; Liu, J.; Welch, C. J. Support of academic synthetic chemistry using separation technologies from the pharmaceutical industry. Org. Biomol. Chem. 2014, 12, 2161-2166.
133. Breslow, R.; Campbell, P. Selective aromatic substitution within a cyclodextrin mixed complex. J. Am. Chem. Soc. 1969, 91, 3085-3085.
134. Breslow, R.; Campbell, P. Selective aromatic substitution by hydrophobic binding of a substrate to a simple cyclodextrin catalyst. Bioorg. Chem. 1971, 1, 140-156.
135. Hoarau, M.; Hureau, C.; Gras, E.; Faller, P. Coordination complexes and biomolecules: A wise wedding for catalysis upgrade. Coord. Chem. Rev. 2015, 308, 445.
136. Marchi-Delapierre, C.; Rondot, L.; Cavazza, C.; Menage, S. Oxidation Catalysis by Rationally Designed Artificial Metalloenzymes. Isr. J. Chem. 2015, 55, 61-75.
137. Hyster, T. K.; Knoerr, L.; Ward, T. R.; Rovis, T. Biotinylated Rh(III) Complexes in Engineered Streptavidin for Accelerated Asymmetric C-H Activation. Science 2012, 338, 500-503.
138. McIntosh, J. A.; Coelho, P. S.; Farwell, C. C.; Wang, Z. J.; Lewis, J. C.; Brown, T. R.; Arnold, F. H. Enantioselective Intramolecular C-H Amination Catalyzed by Engineered Cytochrome P450 Enzymes In Vitro and In Vivo. Angew. Chem., Int. Ed. 2013, 52, 9309-9312.
139. Bordeaux, M.; Singh, R.; Fasan, R. Intramolecular C(sp3-H amination of arylsulfonyl azides with engineered and artificial myoglobin-based catalysts. Bioorg. Med. Chem. 2014, 22, 5697-5704.
140. Hyster, T. K.; Farwell, C. C.; Buller, A. R.; McIntosh, J. A.; Arnold, F. H. Enzyme-Controlled Nitrogen-Atom Transfer Enables Regiodivergent C-H Amination. J. Am. Chem. Soc. 2014, 136, 15505-15508.
141. Singh, R.; Bordeaux, M.; Fasan, R. P450-Catalyzed Intramolecular sp3 C-H Amination with Arylsulfonyl Azide Substrates. ACS Catal. 2014, 4, 546-552.
142. Singh, R.; Kolev, J. N.; Sutera, P. A.; Fasan, R. Enzymatic C(sp3)-H Amination: P450-Catalyzed Conversion of Carbonazidates into Oxazolidinones. ACS Catal. 2015, 5, 1685-1691.
143. Ye, B.; Cramer, N. Chiral Cyclopentadienyl Ligands as Stereocontrolling Element in Asymmetric C-H Functionalization. Science 2012, 338, 504-506.
144. Ichinose, M.; Suematsu, H.; Yasutomi, Y.; Nishioka, Y.; Uchida, T.; Katsuki, T. Enantioselective Intramolecular Benzylic C-H Bond Amination: Efficient Synthesis of Optically Active Benzosultams. Angew. Chem., Int. Ed. 2011, 50, 9884-9887.
145. Liang, C. G.; Collet, F.; Robert-Peillard, F.; Muller, P.; Dodd, R. H.; Dauban, P. Toward a synthetically useful stereoselective C-H amination of hydrocarbons. J. Am. Chem. Soc. 2008, 130, 343-350.