Since Maryland
Submitted
ChemRxiv. Preprint. doi.org/10.1021/jacs.9b07575
Design and Development of Fe-Catalyzed Intra- and Intermolecular Carbofunctionalization of Vinyl Cyclopropanes
Liu, L.; Lee, W.; Yuan, M.; Acha, C.; Geherty, M. B.; Williams, B. Gutierrez, O.
Mechanistic Study of Metallaphotoredox Catalytic Cross-Coupling of Tertiary Radicals and Aryl Halides
Yuan, M.; Song, Z.; Molander, G. A.; Gutierrez, O.
Published
Mechanism of Iminium Salt-Catalyzed C(sp3)-H Amination: Factors Controlling Hydride Transfer versus H-Atom Abstraction
Rotella, M. E.; Der, R.; Hilinski, M. K.; Gutierrez, O.
43. Organometallics 2019, ASAP.
Siloxide Podand Ligand as a Scaffold for Molybdenum Catalyzed Alkyne Metathesis and Isolation of a Dynamic
Metallatetrahedrane Intermediate
Thompson, R. R.; Rotella, M. E.; Du, P.; Zhou, X.; Fronczek, F. R.; Kumar, R.; Gutierrez, O.; Lee, S.
42. ACS Catal. 2019, 9, 8835-8842.
Oxa- and Azabenzonorbornadienes as Electrophilic Partners under Photoredox/Nickel Dual Catalysis
Luo.; Gutierrez-Bonet, A.; Matsui, J. K.; Rotella, M. E.; Dykstra, R.; Gutierrez, O.; Molander, G. A.
41. J. Am. Chem. Soc. 2019, 141, 14843-14852.
The Role of Trichloroacetimidate To Enable Iridium-Catalyzed Regio- and Enantioselective Allylic Fluorination: A Combined
Experimental and Computational Study
Sorlin, A. M.; Mixdorf, J. C.; Rotella, M.; Martin, R.; Gutierrez, O.; Nguyen, H. M.
The Role of Iodanyl Radicals as Critical Chain Carriers in Aerobic Hypervalent Iodine Chemistry
Hyun, S.-M.; Yuan, M.; Maity, A.; Gutierrez, O.; Powers, D. C.
39. Tetrahedron. 2018, 75, 129-136.
Radical-clock α-halo-esters as mechanistic probes for bisphosphine iron-catalyzed cross-coupling reactions
Liu, L.; Lee, W.; Zhou, J.; Bandyopadhyay, S.; Gutierrez, O.
38. Org. Biomol. Chem. 2018, 17, 1767-1772.
Mechanism of Nitrones and Allenoates Cascade Reactions for the Synthesis of Dihydro[1,2-a]indoles
Lee, W.; Yuan, M.; Acha. C.; Onwu, A.; Gutierrez, O.
37. Angew. Chem. Int. Ed. 2018, 57, 17146-17150.
Templating and Catalyzing [2 + 2] Photocycloaddition in Solution Using a Dynamic G‐Quadruplex
Sutyak, K. B.; Lee, W.; Zavalij, P. V.; Gutierrez, O.; Davis, J. T.
Abstract: A templating/covalent capture strategy enables photochemical formation of eight cyclobutanes in one noncovalent
assembly. KI and 16 units of 5′‐cinnamate guanosine form a G‐quadruplex where C=C bonds in neighboring G4‐quartets are
separated by 3.3 Å, enabling [2+2] photocycloaddition in solution. This reaction is high‐yielding (>90 %), regio‐ and
diastereoselective.
36. Comment. Inorg. Chem. 2018, 38, 210-237.
Mechanisms of Bisphosphine Iron-Catalyzed C(sp2)-C(sp3) Cross-Coupling Reactions: Inner-Sphere or Outer-Sphere Arylation?
(invited contribution)
Liu, L; Lee, W; Yuan, M.; Gutierrez, O.
Abstract: In this comment, we present recent insights into the mechanism of bisphosphine-iron catalyzed C(sp2)-C(sp3) cross-
coupling reactions (CCRs) with focus on the nature of the C-C bond formation event (inner sphere versus outer sphere) as revealed
by quantum mechanical calculations from our group and others. Implications toward reaction and catalyst design principles are
discussed.
35. Angew. Chem. Int. Ed. 2018, 57, 15847-15851.
Photoredox/Nickel-Catalyzed Single-Electron Tsuji-Trost Reaction: Development and Mechanistic Insight
Matsui, J.; Gutierrez-Bonet, A.; Rotella, M.; Alam, R.; Gutierrez, O.; Molander, G. A
Abstract: A regioselective, nickel‐catalyzed photoredox allylation of secondary, benzyl, and α‐alkoxy radical precursors is disclosed. Through this manifold, a variety of linear allylic alcohols and allylated monosaccharides are accessible in high yields under mild
reaction conditions. Quantum mechanical calculations [DFT and DLPNO‐CCSD(T)] support the mechanistic hypothesis of a Ni0 to
NiII oxidative addition pathway followed by radical addition and inner‐sphere allylation.
Highlighted in SYNFACTS by Paul Knochel and Juri Skotnitzki! LINK
34. Org. Lett. 2018, 20 6539-6543.
Divergent Reactivity in Pd-Catalyzed [3,3]-Sigmatropic Rearrangement of Allyloxy- and Propargyloxyindoles Revealed by
Computation and Experiment
Gutierrez, O.; Hendrick, C. E.; Kozlowski, M. C.
33. J. Am. Chem. Soc. 2018, 140, 8037-8047.
Redox-Neutral Photocatalytic Cyclopropanation via Radical/Polar Crossover
Abstract: A benchtop stable, bifunctional reagent for the redox-neutral cyclopropanation of olefins has been developed.
Triethylammonium bis(catecholato)iodomethylsilicate can be readily prepared on multigram scale. Using this reagent in combination
with an organic photocatalyst and visible light, cyclopropanation of an array of olefins, including trifluoromethyl- and pinacolatoboryl-
substituted alkenes, can be accomplished in a matter of hours. The reaction is highly tolerant of traditionally reactive functional
groups (carboxylic acids, basic heterocycles, alkyl halides, etc.) and permits the chemoselective cyclopropanation of polyolefinated
compounds. Mechanistic interrogation revealed that the reaction proceeds via a rapid anionic 3-exo-tet ring closure, a pathway
consistent with experimental and computational data.
Highlights: Featured in the top 10 "Most Read Articles" in July 2018! The list covers the top 20 most dowloaded articles in
the previous 30 days of The Journal of American Chemical Society (accessed July 8, 2018).
Highlighted in SYNFACTS by Paul Knochel and Moritz Balkenhohl! LINK
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32. Chem. Sci. 2018, 9, 3186-3191.
Engaging Sulfinate Salts via Ni/Photoredox Dual Catalysis Enables Facile Csp2–SO2R Coupling
Cabrera-Afonso, M. J.; Lu,Z.-P.; Kelly, C. B.; Lang, S. B.; Dykstra, R.; Gutierrez, O.; Molander, G. A.
Abstract: This report details the development and implementation of a strategy to construct aryl- and heteroaryl
sulfones via Ni/photoredox dual catalysis. Using aryl sulfinate salts, the C–S bond can be forged at room temperature under base-free
conditions. An array of aryl- and heteroaryl halides are compatible with this approach. The broad tolerance and mild nature of the
described reaction could potentially be employed to prepare sulfones with biological relevance (e.g., in bioconjugation, drug substance
synthesis, etc.) as demonstrated in the synthesis of drug-like compounds or their precursors. When paired with existing Ni/photoredox
chemistry for Csp3–Csp2 cross-coupling, an array of diverse sulfone scaffolds can be readily assembled from bifunctional
electrophiles. A mechanistic manifold consistent with experimental and computational data is presented.
31. Adv. Synth. Catal. 2018, 360, 1426-1432.
A Simple Procedure for the Synthesis of β -Hydroxyallenamides via Homoallenylation of Aldehydes
Kim, B.-S.; Gutierrez, O.; Kozlowski, M.; Walsh, P. J.
2017
30. J. Am. Chem. Soc. 2017, 139, 16126-16133.
Lee, W.; Zhou, J.; Gutierrez, O.
Abstract: Quantum mechanical calculations are employed to investigate the mechanism and origin of stereoinduction in asymmetric iron-catalyzed C(sp2)-C(sp3) cross-coupling reaction between Grignard reagents and α-chloroesters. A coherent mechanistic picture of this transformation and model for stereoinduction is revealed. These results have broad implications for understanding the mechanisms of iron-catalyzed cross-coupling reactions and rational design of novel iron-based catalysts for asymmetric transformations
PRE-University of Maryland
29. Org. Lett. 2017, 19, 5064-6067.
A Computational Investigation of the Ligand-Controlled Cu-Catalyzed Site-Selective Propargylation and Allenylation of Carbonyl
Zhou, Y.; Gutierrez, O.; Sader, A. C.; Patel, N. D.; Fandrick, D. R.; Busacca, C. A.; Frandrick, K. R.; Kozlowski, M.; Senanayake, C.
H. H.
28. Nature Chem. 2017, 9, 997-1004.
Transition-metal-free chemo- and regioselective vinylation of azaallyls
Li, M.; Gutierrez, O.; Berritt, S.; Pascual-Escudero, A.; Yeşilçimen, A.; Yang, X.; Adrio, J.; Huang, G.; Nakamaru-Ogiso,
E.; Kozlowski, M. C.; Walsh, P. J.
Highlighted in Phys.Org (link:
2016
27. J. Am. Chem. Soc. 2016, 138, 15473-15481.
Wei, X.;Qu, B.; Zeng, X.; Savoie, J.; Fandrick, K. R.; Desrosiers, J.-N.; Tcyrulnikov, S.; Marsini, M. A.; Buono, F. G.; Li, Z.; Yang,
B.-S.; Tang, W.; Haddad, N.; Gutierrez, O.; Wang, J.; Lee, H.; Ma, S.; Campbell, S.; Lorenz, J. C.; Eckhardt, M.; Himmelsbach, F.;
Peters, S.; Patel, N. D.; Tan, Z.; Yee, N. K.; Song, J. J.; Roschangar, F.; Kozlowski, M. C.; Senanayake, C. H.
26. Chem. Sci, 2016, 7, 5581-5586.
Nickel-Catalyzed C-3 Direct Arylation of Pyridinium Ions for the Synthesis of 1-Azafluorenes
Desrosiers, J. N.; Wei, X.; Gutierrez, O.; Savoie, J.; Qu, B.; Zeng, X.; Lee, H.; Grinberg, N.; Haddad, N.; Yee, N. K.; Roschangar, F.; Song, J. J.; Kozlowski, M. C.; Senanayake, C. H.
25. Magn. Reson. Chem. 2016, DOI: 10.1002/mrc.4466
Application of a Computer-assisted Structure Elucidation Program for the Structural Determination of a New Terpenoid Aldehyde with an Unusual Skeleton
Li, X.-N.; Ridge, C. D.; Mazzola, E. P.; Sun, J.; Gutierrez, O.; Moser, A.; DiMartino, J. C.; MacDonald, S. A.; Chen, P.
24. J. Am. Chem. Soc. 2016, 138, 3631-3634.
Dynamically Complex [6+4] and [4+2] Cycloadditions in the Biosynthesis of Spinosyn A
Patel, A.; Chen, Z.; Yang, Z.; Gutierrez, O.; Liu, H.-v.; Houk, K. N.; Singleton, D. A.
23. J. Am. Chem. Soc. 2016, 138, 487-490.
Mechanism of Rh2(II)-Catalyzed Indole Formation—The Catalyst Does Not Control Product Selectivity
Harrison, G. J.; Gutierrez, O.; Jana, N.; Driver, T.; Tantillo, D. J.
2015
22. J. Am. Chem. Soc. 2015, 137, 11491-11497.
Catalytic Kinetic Resolution of Disubstituted Piperidines by Enantioselective Acylation: Synthetic Utility and Mechanistic Insights
Wanner, B.; Kreituss, I.; Gutierrez, O.; Kozlowski, M. C.; Bode, J. W.
21. J. Am. Chem. Soc. 2015, 137, 4896-4899.
Nickel-Catalyzed Cross-Coupling of Photoredox Generated Radicals: Uncovering a General Manifold for Stereoconvergence
in Nickel-Catalyzed Cross-Couplings
Gutierrez, O.; Tellis, J. C.; Primer, D. N.; Molander, G. A.; Kozlowski, M. C.
20. Org. Lett. 2015, 17, 1742-1745.
Development and Origin of Diastereoselectivity of a Practical and Asymmetric Route to Sitagliptin and Derivatives
Gutierrez, O.; Dattatray, M.; Dwivedi, M.; Gudimalla, N.; Chandrashekar, E. R. R.; Vilas, D. H.; Bhattacharya, A.; Bandichhor, R.;
Kozlowski, M. C.
19. BOOK: Understanding Organometallic Reaction Mechanisms and Catalysis. Editor Valentin Ananikov. Wiley-VCH. Weinheim 2015.
Computational Studies on Sigmatropic Shifts via Alkene and Alkyne Activation by Palladium and Gold
Gutierrez, O.; Kozlowski, M. C.
2014
18. J. Am. Chem. Soc. 2014, 136, 11783-11791.
Concerted Amidation of Activated Esters: Reaction Path and Origins of Selectivity in the Kinetic Resolution of Cyclic Amines via
NHC and Hydroxamic Acid Co-Catalyzed Acyl Transfer
Allen, S. E.; Hsieh, S.-Y.; Gutierrez, O.; Bode, J. W.; Kozlowksi, M. C.
17. Organometallics, 2014, 33, 5371-5377 .
Alkenes as Chelating Groups in Diastereoselective Additions of Organometallics to Ketones
Raffier, L.; Gutierrez, O.; Stanton, G. R.; Kozlowski, M. C.; Walsh, P. J.
16. Org. Lett. 2014, 16, 468-471.
Stereocontrol in Asymmetric SE’ Reactions of γ-Substituted α,β-Unsaturated Aldehydes
Williams, D. R.; Atwater, B, A.; Ke, P.; Gutierrez, O.; Tantillo, D. J.
2013
15. Angew. Chem. Int. Ed. 2013, 53, 1279-1282.
Through-Bond/Through-Space Anion Relay Chemistry Exploiting Vinylepoxides as Bifunctional Linchpins
Chen, M. Z.; Gutierrez, O.; Smith III, A. B.
14. Chem. Sci. 2013, 4, 3997-4003.
Mechanism of Triflimide-Catalyzed [3,3]-Sigmatropic Rearrangements of N-Allylhydrazones – Predictions and Experimental
Validation
Gutierrez, O.; Strick, B, F.; Thomson, R. J.; Tantillo, D. J.
13. Chem. Sci. 2013, 4, 3894-3898.
Carbonium vs. Carbenium Ion-like Transition State Geometries for Carbocation Cyclization – How Strain Associated with
Bridging Affects 5-exo vs. 6-endo Selectivity
Gutierrez, O.; Harrison, J. G.; Felix, R. J.; Guzman, F. C.; Gagné, M. R.; Tantillo, D. J.
12. J. Org. Chem. 2013, 78, 5685-5690.
Gold(I)-Catalyzed Formation of Bicyclo[4.2.0]oct-1-enes
Felix, R. J.; Gutierrez, O.; Tantillo, D. J.; Gagné, M. R.
11. J. Org. Chem. 2013, 78, 4744-4761.
Mild Aromatic Palladium-Catalyzed Protodecarboxylation: Kinetic Assessment of the Decarboxylative Palladation and the
Protodepalladation Steps
Dickstein, J. S.; Curto, J. M.; Gutierrez, O.; Mulrooney, C. A.; Kozlowski, M. C.
2012
10. Nature Chem. 2012, 4, 405-409.
A Au-Catalyzed Enantioselective Cope Rearrangement of Achiral 1,5- Dienes
Felix, R. J.; Weber, D.; Gutierrez, O.; Tantillo, D. J.; Gagné, M. R.
09. J. Org. Chem. 2012, 77, 8845-8850.
Analogies Between Synthetic and Biosynthetic Reactions in which [1,2]-Alkyl Shifts are Combined with Other Events-Dyotropic,
Schmidt and Carbocation Rearrangements
Gutierrez, O.; Tantillo, D. J.
08. Chem. Eur. J. 2012, 18, 11029-11035.
Reexamining the Mechanisms of Competing [3,3] and [3,5] Sigmatropic Shifts of 1,3,7-Octatriene
Gutierrez, O.; Harrison, J. G.; Pemberton, R. P.; Tantillo, D. J.
07. J. Am. Chem. Soc. 2012, 134, 6528-6531.
Stereocontrol in a Combined Allylic Azide Rearrangement and Intramolecular Schmidt Reaction: Application to Asymmetric
Synthesis of Pinnaic Acid
Liu, R.; Gutierrez, O.; Tantillo, D. J.; Aubé, J.
06. J. Mass Spectrom. 2012, 47, 676-686.
Fragmentation of Oxime and Silyl-oxime Ether Odd-electron Positive Ions by the McLafferty Rearrangement: New Insights on
Structural Factors that Promote α, β-Fragmentation
Laulhe, S.; Bogdanov, B.; Johannes, L. M.; Gutierrez, O.; Harrison, J. G.; Tantillo, D. J.; Zhang, X.; Nantz, M. H.
05. J. Org. Chem. 2012, 77, 640-647.
Mechanism of the Acid Promoted Intramolecular Schmidt Reaction. Theoretical Assessment of the Importance of Lone
Pair-Cation, Cation-pi and Steric Effects in Controlling Regioselectivity
Gutierrez, O.; Aubé, J.; Tantillo, D. J.
2010
04. Organometallics 2010, 29, 3541-3545.
Transition Metal Intervention for a Classic Reaction - Assessing the Feasibility of Ni(0)- promoted [1,3] Sigmatropic Shifts of
Bicyclo[3.2.0]hept-2-enes
Gutierrez, O.; Tantillo, D. J.
03. J. Org. Chem. 2010, 75, 6933-6940.
Synthesis of a trans, syn, trans-Dodecahydrophenanthrene via a Bicyclic Transannular Diels-Alder Reaction: Intermediate for the
Synthesis of Fusidic Acid
Jung, M E.; Zhang, T.-H.; Lui, R. M.; Gutierrez, O.; Houk, K. N.
02. J. Am. Chem. Soc. 2010, 132, 6001-6005.
Nature of Intermediates in Organo-SOMO Catalysis of α-Arylation of Aldehydes
Um, J. M.; Gutierrez, O.; Schoenebeck, F.; Houk, K. N.; MacMillan. D. W. C.
2009
01.Org. Lett. 2009, 11, 4298-4301.
Origin of Stereoselectivity in the Imidazolidinone-Catalyzed Reductions of Cyclic α, β- Unsaturated Ketones
Gutierrez, O.; Iafe, R.; Houk, K. N.
