Since Maryland   

​

Submitted 

​

46. 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. 

​

45. Submitted.

      Mechanistic Study of Metallaphotoredox Catalytic Cross-Coupling of Tertiary Radicals and Aryl Halides

      Yuan, M.; Song, Z.; Molander, G. A.; Gutierrez, O. 

​

44. Submitted.

      Mechanism of Iminium Salt-Catalyzed C(sp3)-H Amination: Factors Controlling Hydride Transfer versus H-Atom Abstraction

      Rotella, M. E.; Hilinski, M. K.; Gutierrez, O. 

​

Published

​

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. 

​

​

​

40. Chem, 2019, 5, 2388-2404

      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. 

​

​

​

​

​

​

​

​

​

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​

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​

​

 

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

      Phelan, J. P.; Lang, S. B.; Compton, J. S.; Kelly, C. B.; Dykstra, R.; Gutierrez, O.; Molander, G. A.

 

 

 

 

 

 

 

 

 

    

      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     

      Highlighted in Organic Chemistry Portal by Reto Muellerl! LINK   

 

 

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.  

      Mechanism of Nakamura’s Bisphosphine Iron-Catalyzed Asymmetric C(sp2)-C(sp3) Cross-Coupling Reaction: The Role of Spin in

      Controlling Arylation Pathway

      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        

      Compounds

      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.

      Sequential C-H Arylation and Enantioselective Hydrogenation Enables Ideal Asymmetric Entry to the Indenopiperidine Core of an  

      11β-HSD-1 Inhibitor

      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.