Engl, P. S.; Santiago, C. B.; Gordon, C. P.; Liao, W.-C.; Fedorov, A.; Copéret, C.; Sigman, M. S.; Togni, A. "Exploiting and Understanding the Selectivity of Ru-N-Heterocyclic Carbene Metathesis Catalysts for the Ethenolysis of Cyclic Olefins to α,ω-Dienes" J. Am. Chem. Soc.2017DOI: 10.1021/jacs.7b06947


Orlandi, M.; Hilton, M. J.; Yamamoto, E.; Toste, F. D.; Sigman, M. S. "Mechanistic Investigations of the Pd(0)-Catalyzed Enantioselective 1,1-Diarylation of Benzyl Acrylates" J. Am. Chem. Soc.2017DOI: 10.1021/jacs.7b06917


Niemeyer, Z. L.; Pindi, S.; Khrakovsky, D. A.; Kuzniewski, C. N.; Hong, C. M.; Joyce, L. A.; Sigman, M. S.; Toste, F. D. "Parameterization of Acyclic Diaminocarbene Ligands Applied to a Gold(I)-Catalyzed Enantioselective Tandem Rearrangement/Cyclization" J. Am. Chem. Soc.2017DOI: 10.1021/jacs.7b08791


 Keylor, M. H.; Niemeyer, Z. L.; Sigman, M. S.; Tan, K. L."Inverting Conventional Chemoselectivity in Pd-Catalyzed Amine Arylations with Multiply Halogenated Pyridines" J. Am. Chem. Soc.2017DOI: 10.1021/jacs.7b05409


 Guo, J.-Y.; Minko, Y.; Santiago, C. B.; Sigman, M. S. "Developing Comprehensive Computational Parameter Sets To Describe the Performance of Pyridine-Oxazoline and Related Ligands" ACS Catal. 2017, 7, 4144.


Mack, J. B. C.; Gipson, J. D.; Du Bois, J.; Sigman, M. S. "Ruthenium-Catalyzed C–H Hydroxylation in Aqueous Acid Enables Selective Functionalization of Amine Derivatives" J. Am. Chem. Soc.2017 DOI: 10.1021/jacs.7b05469 


Plata, R. E.; Hill, D. E.; Haines, B. E.; Musaev, D. G.; Chu, L.; Hickey, D. P.; Sigman, M. S.; Yu, J.-Q.; Blackmond, D. G. "A Role for Pd(IV) in Catalytic Enantioselective C–H Functionalization with Monoprotected Amino Acid Ligands under Mild Conditions" J. Am. Chem. Soc.2017, 139, 9238.


 Orlandi, M.; Coelho, J. A. S.; Hilton, M. J.; Toste, F. D.; Sigman, M. S. "Parametrization of Non-covalent Interactions for Transition State Interrogation Applied to Asymmetric Catalysis" J. Am. Chem. Soc.2017, 139, 6803.


Christian, A. H.; Niemeyer, Z. L.; Sigman, M. S.; Toste, F. D. "Uncovering Subtle Ligand Effects of Phosphines Using Gold(I) Catalysis" ACS Catal. 2017, 3973.


 Avila, C. M.; Patel, J. S.; Reddi, Y.; Saito, M.; Nelson, H. M.; Shunatona, H. P.; Sigman, M. S.; Sunoj, R. B.; Toste, F. D. "Enantioselective Heck–Matsuda Arylations through Chiral Anion Phase-Transfer of Aryl Diazonium Salts" Angew. Chem. Int. Ed.2017, DOI: 10.1002/anie.201702107


 Chen, Z.-M.; Nervig, C. S.; DeLuca, R. J.; Sigman, M. S.* "Palladium-Catalyzed Enantioselective Redox-Relay Heck Alkynylation of Alkenols to Access Propargylic Stereocenters” Angew. Chem. Int. Ed.2017, 56, 1.


 B. P. Woods, M. Orlandi, C.-Y. Huang, M. S. Sigman, A. G. Doyle "Nickel-Catalyzed Enantioselective Reductive Cross-Coupling of Styrenyl Aziridines" J. Am. Chem. Soc. 2017, 1395688.


Toste, F. D.; Sigman, M. S.; Miller S. J. "Pursuit of Noncovalent Interactions for Strategic Site-Selective Catalysis" Acc. Chem. Res. 2017, 50, 609.


Neel, A. J.; Hilton,M. J.; Sigman, M. S.; Toste,F. D. "Exploiting non-covalent π interactions for catalyst design" Nature 2017, 543, 637.

nature rev

Liu, Y.; Hickey, D. P.; Guo, J.-Y.; Earl, E.; Abdellaoui, S.; Milton, R. D.; Sigman, M. S.*; Minteer, S. D.*; Calabrese Barton, S.* "Substrate Channeling in an Artificial Metabolon: A Molecular Dynamics Blueprint for an Experimental Peptide Bridge," ACS Catal. 2017, 2486.

substrate channeling

Thornbury, R. T.; Saini, V.; Fernandes, T. d. A.; Santiago, C. B.; Talbot, E. P. A.; Sigman, M. S.; McKenna, J. M.; Toste, F. D.* "The development and mechanistic investigation of a palladium-catalyzed 1,3-arylfluorination of chromenes," Chem. Sci.  2017, DOI: 10.1039/c6sc05102b

Toste pub

Sevov, C. S.; Hickey, D. P.; Cook, M. E.; Robinson, S. G.; Barnett, S.; Minteer, S. D.*; Sigman, M. S.*; Sanford, M. S.* " Physical Organic Approach to Persistent, Cyclable, Low-Potential Electrolytes for Flow Battery Applications," J. Am. Chem. Soc. 2017139, 2924.


Zhang, C.; Tutkowski, B.; DeLuca, R. J.; Joyce, L. A.  Wiest, O.; Sigman, M. S.* "Palladium-catalyzed enantioselective Heck alkenylation of trisubstituted allylic alkenols: a redox-relay strategy to construct vicinal stereocenters," Chem. Sci.  2017, 8, 2277.



 Hilton, M.; Sigman, M. S.* "(S)-4-(tert-Butyl)-2-[4-(trifluoromethyl) pyridin-2-yl]-4,5-dihydrooxazole," Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons, Ltd: 2016.

 Race, N. J.; Schwalm, C. S.; Nakamuro, T.; Sigman, M. S.* "Palladium-Catalyzed Enantioselective Intermolecular Coupling of Phenols and Allylic Alcohols," J. Am. Chem. Soc. 2016, 138, 15881.


Nick TOC

Eiji, Y.; Hilton, M. J.; Orlandi, M.; Saini, V.; Toste, F.D.; Sigman, M. S.* "Development and Analysis of a Pd(0)-Catalyzed Enantioselective Diarylation of Acrylates Enabled by Chiral Anion Phase Transfer," J. Am. Chem. Soc. 2016, 138, 15877.


Marg TOC

 Patel, H. H.; Sigman, M.S.* "Enantioselective Palladium-Catalyzed Alkenylation of Trisubstituted Alkenols to Form Allylic Quaternary Centers," J. Am. Chem. Soc. 2016,138, 14226. 

harsh TOC

 Santiago, C. B.; Milo, A; Sigman, M. S.* "Developing a Modern Approach To Account for Steric Effects in Hammett-Type Correlations," J. Am. Chem. Soc. 2016, 138, 13424.


celine TOC

 Chen, Z.-M.; Hilton, M. J.; Sigman, M. S.* "Palladium-Catalyzed Enantioselective Redox-Relay Heck Arylation of 1,1-Disubstituted Homoallylic Alcohols," J. Am. Chem. Soc.2016, 138, 11461.

 zhi min TOC

Xu,L.; Zhang, X.; McCammant, M. S.; Sigman, M. S.; Wu, Y.-D.; Wiest, O.* "Mechanism and Selectivity in the Pd-Catalyzed Difunctionalization of Isoprene," J. Org. Chem2016, 81, 7604.

Matt TOC

Sigman, M. S.*; Harper, K. C.;  Bess, E. N.; Milo, A. "The Development of Multidimensional Analysis Tools for Asymmetric Catalysis and Beyond," Acc. Chem. Res.201649, 1292–1301.


McCammant, M. S.; Shigeta, T; Sigman, M. S.* "Palladium-Catalyzed 1,3-Difunctionalization Using Terminal Alkenes with Alkenyl Nonaflates and Aryl Boronic Acids," Org. Lett. 2016, 18, 1792–1795.


Niemeyer, Z.; Milo, A.; Hickey, D. P.; Sigman, M. S.* "Parameterization of phosphine ligands reveals mechanistic pathways and predicts reaction outcomes," Nature Chem. 2016, 8610–617.

Zach TOC

Neel, A. J.; Milo, A.; Sigman, M. S.; Toste, F. D. "Enantiodivergent Fluorination of Allylic Alcohols: Data Set Design Reveals Structural Interplay between Achiral Directing Group and Chiral Anion," J. Am. Chem. Soc., 2016, 138, 3863-3875.


 Wheeldon, I.*; Minteer, S.D.; Banta, S.; Barton, S.C.; Atanassov, P.; Sigman, M. S. "Substrate channelling as an approach to cascade reactions," Nature Chemistry, 2016, 8, 299-309.

Weldy, N. M.; Schafer, A. G.; Owens, C. P.; Herting, C. J.; Varela-Alvarez, A.; Chen, S.; Niemeyer, Z.; Musaev, D. G.; Sigman, M. S.; Davies, H. M. L.; Blakey, S. B. "Iridium(III)-bis(imidazolinyl)phenyl catalysts for enantioselective C–H functionalization with ethyl diazoacetate," Chem. Sci. 2016, 7, 3142–3146.



Zhang, C.; Santiago, C. B.; Crawford, J. M.; Sigman, M. S.* “Enantioselective Dehydrogenative Heck Arylations of Trisubstituted Alkenes with Indoles to Construct Quaternary Stereocenters,” J. Am. Chem. Soc. 2015, 137, 15668.



Hickey, D. P.; Schiedler, D. A.; Matanovic, I.;Doan, P. V.; Atanassov, P.; Minteer, S. D.*; Sigman, M. S.* “Predicting Electrocatalytic Properties: Modeling Structure-Activity Relationships of Nitroxyl Radicals,” J. Am. Chem. Soc. 2015, 137, 16179-16186.



Hickey, D. P.; Milton, R. D.; Chen, R.; Sigman, M. S.*; Minteer, S. D.* “TEMPO-Modified Linear Poly(ethylenimine) for Immobilization-Enhanced Electrocatalytic Oxidation of Alcohols,” ACS Catalysis 2015, 5, 5519-5524.



Zhang, C.; Santiago, C. B.; Kou, L.; Sigman, M. S.* “Alkenyl Carbonyl Derivatives in Enantioselective Redox Relay Heck Reactions: Accessing α,β-Unsaturated Systems,” J. Am Chem. Soc. 2015, 137, 7290-7293.



Mougel, V.; Santiago, C. B.; Zhizhko, P. A.; Bess, E. N.; Varga, J.; Frater, G.; Sigman, M. S.; Copéret, C. “Quantitatively Analyzing Metathesis Catalyst Activity and Structural Features in Silica-Supported Tungsten Imido–Alkylidene Complexes,” J. Am. Chem. Soc. 2015, 137, 6699-6704.



Hilton, M. J.; Cheng, B.; Buckley, B. R.; Xu, L.; Wiest, O.; Sigman, M. S.* “Relative reactivity of alkenyl alcohols in the palladium-catalyzed redox-relay Heck reaction,” Tetrahedron (invited special issue honoring Tsuji), 2015, in press.



Bess, E. N.; Guptill, D. M.; Davies, H. M. L.*; Sigman, M. S.* “Using IR Vibrations to Quantitatively Describe and Predict Site-Selectivity in Multivariate Rh-Catalyzed C–H Functionalization,” Chem. Sci. 2015, 6, 3057-3062.



Saini, V.; O’Dair, M. §; Sigman, M. S.* “Synthesis of Highly Functionalized Tri-and Tetrasubstituted Alkenes via Pd-Catalyzed 1,2-Hydrovinylation of Terminal 1,3-Dienes,” J. Am. Chem. Soc. 2015, 137, 608-611.



Patel, H. H.; Sigman, M.S.* "Palladium-Catalyzed Enantioselective Heck Alkenylation of Acyclic Alkenols Using a Redox-Relay Strategy," J. Am. Chem. Soc.2015,137, 3462-3465.



Milo, A., Neel, A. J.; Toste, F. D.*; Sigman, M. S.* “A Data-Driven Approach to Mechanistic Elucidation in Chiral Anion Catalysis,” Science, 2015, 347, 737-743. 



McCammant, M.S.; Sigman, M.S.* "Development and investigation of a site selective palladium-catalyzed 1,4-difunctionalization of isoprene using pyridine–oxazoline ligands" Chem. Sci.2015, 6, 1355-1361.



Hilton, M. J.; Xu, L.-P.; Norrby, P.-O.; Wu, Y.-D.; Wiest, O.; Sigman, M. S.* “Investigating the Nature of Palladium Chain-Walking in the Enantioselective Redox-Relay Heck Reaction of Alkenyl Alcohols,” J. Org. Chem. 2014, 79, 11841-11850.

Hilton JOC TOC Graphic


Stokes, B. J.; Liao, L.; de Andrade, A. §; Wang, Q.; Sigman, M. S.* “A Palladium-Catalyzed Three-Component-Coupling Strategy for the Differential Vicinal Diarylation of Terminal 1,3-Dienes,” Org. Lett. 2014, 16, 4666-4669.

 Stokes Org Lett TOC Graphic


Bess, E. N.; Bischoff, A. J.§; Sigman, M. S.* “Designer Substrate Library for Quantitative, Predictive Modelling of Reaction Performance,” Proc. Nat. Acad. Sci.2014, 111, 14698-14703.



Vaden, R. M.; Gligorich, K. M.; Jana, R.; Sigman, M. S.; Welm, B. E. “The small molecule C-6 is selectively cytotoxic against breast cancer cells and its biological action is characterized by mitochondrial defects and ER stress,” Breast Cancer Res.,2014, 16, 472.



Hickey, D. P.; McCammant, M. S.; Giroud, F.; Sigman, M. S.*, Minteer, S. D.* “Hybrid Enzymatic and Organic Electrocatalytic Cascade for the Complete Oxidation of Glycerol,” J. Am. Chem. Soc., 2014, 136, 15917-15920.


Hickey JACS TOC Graphic


Michel, B. M.; Steffens, L. D.; Sigman, M. S.* “The Wacker Oxidation” In Organic Reactions Volume 84; Denmark, S. E. Ed., John Wiley & Sons, Inc.: 2014; pp 75-414.



Bess, E. N.; DeLuca, R. J; Tindall, D. J.; Oderinde, M. S.; Roizen, J. L.; Du Bois, J.*; Sigman, M. S.* “Analyzing Site-Selectivity in Rh2(esp)2-Catalyzed Intermolecular C–H Amination Reactions,” J. Am. Chem. Soc. 2014, 136, 5783-5789.

JACS 2014 Dubois

Stokes, B. J.; Bischoff, A. J.; Sigman, M. S.* “Pd(Quinox)-Catalyzed Allylic Relay Suzuki Reactions of Secondary Homostyrenyl Tosylates via Alkene-Assisted Oxidative Addition,” Chem. Sci. 2014, 5, 2336-2339.

chem sci 2014

Mei, T.-S.; Patel, H. H.; Sigman, M. S.* “Enantioselective Construction of Remote Quaternary Stereocenters,” Nature 2014, 508, 340-344.

Nature 2014

 Milo, A.; Bess, E.N.; Sigman, M.S. "Interrogating selectivity in catalysis using molecular vibrations"Nature2014, 507, 210-214.

DeLuca, R.J.; Stokes, B.J.; Sigman, M.S. "The strategic generation and interception of palladium-hydrides for use in alkene functionalization reactions" Pure Appl. Chem.2014, 86, 395-408.

Xu, L.; Hilton, M.J.; Zhang, X.; Norrby, P.-O.; Wu, Y.-D.; Sigman, M.S.; Wiest, O. "Mechanism, Reactivity and Selectivity in Palladium-Catalyzed Redox-Relay Heck Arylations of Alkenyl Alcohols"J. Am. Chem. Soc.2014, 136, 1960-1.


Saini, V.; Stokes, B.J.; Sigman, M.S. "Transition-Metal-Catalyzed Laboratory-Scale Carbon-Carbon Bond-Forming Reactions of Ethylene" Angew. Chem. Int. Ed. 2013, 52, 11206-11220.

Saini, V.; Liao, L.; Wang, Q.; Jana, R.; Sigman, M.S. "Pd(0)-Catalyzed 1,1-Diarylation of Ethylene and Allylic Carbonates"Org. Lett. 2013, 15, 5008-5011.

Gligorich, K.M.; Vaden, R.M.; Shelton, D.N.; Wang, G.; Matsen, C.B.; Looper, R.E.; Sigman, M.S.; Welm, B.E. "Development of a Screen to Identify Selective Small Molecules Active Against Patient-Derived Metastatic and Chemoresistant Breast Cancer Cells"Breast Cancer Research2013, 15.

Mei, T.-S.; Werner, E.W.; Burckle, A.J.; Sigman, M.S. "Enantioselective Redox-Relay Oxidative Heck Arylations of Acyclic Alkenyl Alcohols Using Boronic Acids"J. Am. Chem. Soc.2013, 135, 6830-6833.

Image for publication 94

Harper, K.C.; Sigman, M.S. "Using Physical Organic Parameters to Correlate Asymmetric Catalyst Performance"J. Org. Chem.2013, 78, 2813-2818.

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McCammant, M.S.; Liao, L.; Sigman, M.S. "Palladium-Catalyzed 1,4-Difunctionalization of Butadiene To Form Skipped Polyenes"J. Am. Chem. Soc.2013, 135, 4167-4170.

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Harper, K.C.; Vilardi, S.C.; Sigman, M.S. "Prediction of Catalyst and Substrate Performance in the Enantioselective Propargylation of Aliphatic Ketones by a Multidimensional Model of Steric Effects"J. Am. Chem. Soc.2013, 135, 2482-2485.

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Bess, E.N.; Sigman, M.S. "Distinctive Meta-Directing Group Effect for Iridium-Catalyzed 1,1-Diarylalkene Enantioselective Hydrogenation"Org. Lett.2013, 15, 646-649.

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DeLuca, R.J.; Edwards, J.L.; Steffens, L.D.; Michel, B.W.; Qiao, X.; Zhu, C.; Cook, S.P.; Sigman, M.S. "Wacker-Type Oxidation of Internal Alkenes using Pd(Quinox) and TBHP"J. Org. Chem.2013, 78, 1682-1689.

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DeLuca, R.J.; Sigman, M.S. "The Palladium-Catalyzed Anti-Markovnikov Hydroalkylation of Allylic Alcohol Derivatives"Org. Lett.2013, 15, 92-95.

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Werner, E.W.; Mei, T-S.; Burckle, A.J.; Sigman, M.S. "Enantioselective Heck Arylations of Acyclic Alkenyl Alcohols Using a Redox-Relay Strategy"Science.2012, 338, 1455-1458.

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Jana, R.; Pathak, T.P.; Jensen, K.H.; Sigman, M.S. "Palladium(II)-Catalyzed Enantio- and Diastereoselective Synthesis of Pyrrolidine Derivatives"Org. Lett.2012, 14, 4074-4077.

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Saini, V.; Sigman, M.S. "Palladium-Catalyzed 1,1-Difunctionalization of Ethylene,"J. Am. Chem. Soc.2012, 134, 11372-11375.

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Stokes, B.J.; Opra, S.M.; Sigman, M.S. "Palladium-Catalyzed Allylic Cross-Coupling Reactions of Primary and Secondary Homoallylic Electrophiles,"J. Am. Chem. Soc.2012, 134, 11408-11411.

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Pathak, T.P.; Osiak, J.G.; Vaden, R.M.; Welm, B.E.; Sigman, M.S. "Synthesis and Preliminary Biological Study of Bisindolymethanes Accessed by an Acid-Catalyzed Hydroarylation of Vinylindoles,"Tetrahedron2012, 68, 5203-5208.

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Harper, K.C.; Bess, E.N.; Sigman, M.S. "Multidimensional Steric Parameters in the Analysis of Asymmetric Catalytic Reactions,"Nature Chem.2012, 4, 366-374. News and Views: Miller, S.J. "Asymmetric catalysis: Correlating sterics in catalysis,"Nature Chem.2012, 4, 344.

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Sigman, M.S.; Werner, E.W. "Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C-H Bond Functionalization"Acc. Chem. Res., 2011, 45, 874-884.

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Michel, B.W.; Sigman, M.S. "Peroxide-Mediated Wacker Oxidations for Organic Synthesis,"Aldrichimica Acta, 2011, 44, 55-61.

Pathak, T.P.; Sigman, M.S. "Applications of ortho-Quinone Methide Intermediates in Catalysis and Asymmetric Synthesis,"J. Org. Chem.2011, 76, 9210-9215.

image for publication 80

Harper, K.C.; Sigman, M.S. "Three-Dimensional Correlation of Steric and Electronic Free Energy Relationships Guides Asymmetric Propargylation"Science., 2011, 333, 1875-1878.

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DeLuca, R.J.; Sigman, M.S. "Anti-Markovnikov Hydroalkylation of Allylic Amine Derivatives via a Palladium-Catalyzed Reductive Cross-Coupling Reaction"J. Am. Chem. Soc., 2011, 133, 11454-11457.

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Werner, E. W.; Sigman, M. S. "Operationally Simple and Highly (E)-Styrenyl-Selective Heck Reactions of Electronically Nonbiased Olefins"J. Am. Chem. Soc., 2011, 133, 9692-9695.

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Podhajsky, S. M.; Iwai, Y.; Cook-Sneathen, A.; Sigman, M. S. "Asymmetric Palladium-Catalyzed Hydroarylation of Styrenes and Dienes"Tetrahedron, 2011, 67, 4435-4441.

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Michel, B.W.; Steffens, L.D.; Sigman, M. S. "On the Mechanism of the Palladium-Catalyzed tert-Butylhydroperoxide-Mediated Wacker-Type Oxidation of Alkenes Using Quinoline-2-Oxazoline Ligands"J. Am. Chem. Soc., 2011, 133, 8317-8325.

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Pathak, T. J.; Sigman, M. S. "Palladium-Catalyzed Hydro-functionalization of Vinyl Phenol Derivatives with Heteroaromatics" Org. Lett., 2011, 13, 2774-2777.

McCombs, J. R.; Michel, B.W.; Sigman, M. S. "Catalyst-Controlled Wacker-Type Oxidation of Homoallylic Alcohols in the Absence of Protecting Groups" J. Org. Chem., 2011, 76, 3609-3613.

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Liao, L.; Jana, R.; Urkalan, K.B.; Sigman, M. S. "A Palladium-Catalyzed Three-Component Cross-Coupling of Conjugated Dienes or Terminal Alkenes with Vinyl Triflates and Boronic Acids" J. Am. Chem. Soc., 2011, 133, 5784-5787.

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Jana, R.; Pathak, T. P.; Sigman, M. S. "Advances in Transition Metal (Pd,Ni,Fe)-Catalyzed Cross-Coupling Reactions Using Alkyl- organometallics as Reaction Partners" Chem. Rev., 2011, 111, 1417-1492.

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Harper, K. C.; Sigman, M. S.* "Predicting and Optimizing Asymmetric Catalyst Performance Using the Principles of Experimental Design and Steric Parameters" Proc. Nat. Acad. Sci., 2011, 108, 2179-2183.


Jensen, K. H.; Webb, J. D.; Sigman, M.S. "Advancing the Mechanistic Understanding of an Enantioselective Palladium-Catalyzed Alkene Difunctionalization Reaction" J. Am. Chem. Soc.2010, 132, 17471-17482.

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Jensen, K. H.; Sigman, M.S. "Evaluation of Catalyst Acidity and Substrate Electronic Effects in a Hydrogen Bond-Catalyzed Enantioselective Reaction" J. Org. Chem. 2010, 75, 7194-7201.

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Werner, E.; Sigman, M.S. "A Highly Selective and General Palladium Catalyst for the Oxidative Heck Reaction of Electronically Nonbiased Olefins" J. Am. Chem. Soc. 2010, 132, 13981-13983.

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Michel, B. W.; McCombs, J. R.; Winkler, A.; Sigman, M.S. "Catalyst-Controlled Wacker-Type Oxidation of Protected Allylic Amines" Angew. Chem. Int. Ed. 2010, 49, 7312-7315.

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Anderson, B. J.; Keith, J.A.; Sigman, M.S. "Experimental and Computational Study of a Direct O2-Coupled Wacker Oxidation: Water Dependence in the Absence of Cu Salts" J. Am. Chem. Soc, 2010, 132, 11872-11874.

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Liao, L. Sigman, M.S. "Palladium-Catalyzed Hydroarylation of 1,3-Dienes with Boronic Sters via Reductive Formation of pi-Allyl Palladium Intermediates under Oxidative Conditions" J. Am. Chem. Soc,2010, 132, 10209-10211.

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Pathak, T.P.; Gligorich, K.M.; Welm, B.E.; Sigman, M.S. "Synthesis and Preliminary Biological Studies of 3-Substituted Indoles Accessed by a Palladium-Catalyzed Enantioselective Alkene Difunctionalization Reaction"J. Am. Chem. Soc., 2010, 132, 7870-7871.

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Gustafson, J.L.; Sigman, M.S.; Miller, S.J. "Linear Free-Energy Relationship Analysis of a Catalytic Desymmetrization of a Diarymethane-bis(phenol)"Org. Lett., 2010, 12 (12), 2794-2797.

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Werner, E.W.; Urkalan, K.B.; Sigman, M.S. "PDII-Catalyzed Oxidative 1,1-Diarylation of Terminal Olefins"Org. Lett., 2010, 12 (12), 2848-2851.

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Urkalan, K.B.; Sigman, M.S. "Palladium-Catalyzed Hydroalkylation of Styrenes with Organozinc Reagents To Form Carbon-Carbon sp3-sp3 Bonds under Oxidative Conditions"J. Am. Chem. Soc., 2009, 131 (50), 18042-18043.

Publication 59 Image

Jensen, K.H.; Pathak, T.P.; Zhang, Y.; Sigman, M.S. "Palladium-Catalyzed Enantioselective Addition of Two Distinct Nucleophiles across Alkenes Capable of Quinone Methide Formation"J. Am. Chem. Soc. 2009, 131, 17074-17075.

Sigman, M.S.; Miller, J.J. "Examination of the Role of Taft-Type Steric Parameters in Asymmetric Catalysis"J. Org. Chem.2009, 74 (20), pp 7633-7643.

Publication 57

Gligorich, K.M.; Sigman, M.S. "Recent advancements and challenges of palladiumII-catalyzed oxidation reactions with molecular oxygen as the sole oxidant," Chem. Commun., 2009, , 3854 - 3867.

Publication 56 Image

Gligorich, K.M.; Iwai, Y.; Cummings, S.A.; Sigman, M.S. "A new approach to carbon-carbon bond formation: development of aerobic Pd-catalyzed reductive coupling reactions of organometallic reagents and styrenes,"Tetrahedron, 2009, 65, 26, 5074-5083.

Publication 55 Image

Miller, J.J.; Rajaran, S.; Pfaffenroth, C.; Sigman, M.S. "Synthesis of amine functionalized oxazolines with applications in asymmetric catalysis,"Tetrahedron, 2009, 65, 3110-3119.

Publication 54 Image

Michel, B. W.; Camelio, A. M; Cornell, C. N.; Sigman, M. S. "A General and Efficient Catalyst System for a Wacker-Type Oxidation Using TBHP as the Terminal Oxidant: Application to Classically Challenging Substrates,"J. Am. Chem. Soc.2009, 131, 17, 6076-6077.

Publication 53 Image

Urkalan, K.B.; Sigman, M.S. "Palladium-Catalyzed Oxidative Intermolecular Difunctionalization of Terminal Alkenes using Organostannanes and Molecular Oxygen,”Angew. Chem., Int. Ed.2009, 48, 3146-3149.

Publication 52 Image


Jensen, K. H.; Sigman, M. S. "Mechanistic Approaches to Palladium-Catalyzed Alkene Difunctionalization Reactions,"Org. Biomol. Chem. 2008, 8, 4083-4088.

Publication 51 Image

Iwai, Y.; Gligorich, K. M.; Sigman, M. S. "Aerobic Alcohol Oxidation Coupled to Palladium-Catalyzed Alkene Hydroarylation with Boronic Esters,” Angew. Chem., Int. Ed.2008, 47, 3219-3222.

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Miller, J. J.; Sigman, M. S. "Quantitatively Correlating the Effect of Ligand-Substituent Size in Asymmetric Catalysis Using Linear Free Energy Relationships,”Angew. Chem., Int. Ed.2008, 47, 771-774.


Gligorich, K. M.; Cummings, S. A.; Sigman, M. S. "Palladium-Catalyzed Reductive Coupling of Styrenes and Organostannanes under Aerobic Conditions,”J. Am. Chem. Soc.2007, 129, 14193-14195.


Gligorich, K. M.; Sigman, M. S. "Mechanistic Questions about the Reaction of Molecular Oxygen with Palladium in Oxidase Catalysis,"Angew. Chem., Int. Ed.2006, 45, 6612-6615.

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Schultz, M. J.; Sigman, M. S. "Recent Advances in Homogeneous Transition Metal-Catalyzed Aerobic Alcohol Oxidations,"Tetrahedron2006, 62, 8227-8241.

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Sigman, M. S.; Jensen, D. R. "Ligand-Modulated Palladium-Catalyzed Aerobic Alcohol Oxidations,"Acc. Chem. Res.2006, 39, 221-229.
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Balija, A. M.; Stowers, K. J.; Schultz, M. J.; Sigman, M. S. "Pd(II)-Catalyzed Conversion of Styrene Derivatives to Acetals: Impact of (-)-Sparteine on Regioselectivity,"Org. Lett. 2006, 8, 1121-1124.

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Gligorich, K. M.; Schultz, M. J.; Sigman, M. S. "Palladium(II)-Catalyzed Aerobic Hydroalkoxylation of Styrenes Containing a Phenol," J. Am. Chem. Soc.2006, 128, 2794-2795.
Schultz, M. J.; Sigman, M. S. "Palladium(II)-Catalyzed Aerobic Dialkoxylation of Styrenes: A Profound Influence of an o-Phenol,"J. Am. Chem. Soc.2006, 128, 1460-1461.


Mueller, J. A.; Cowell, A.; Chandler, B. D.; Sigman, M. S. "Origin of Enantioselection in Chiral Alcohol Oxidation Catalyzed by Pd[(-)-sparteine]Cl2,"J. Am. Chem. Soc.2005, 127, 14817-14824.
Schultz, M. J.; Adler, R. S.; Zierkiewicz, W.; Privalov, T.; Sigman, M. S. "Using Mechanistic and Computational Studies to Explain Ligand Effects in the Palladium-Catalyzed Aerobic Oxidation of Alcohols,"J. Am. Chem. Soc.2005, 127, 8499-8507.
Dible, B. R.; Sigman, M. S.; Arif, A. M. "Oxygen-Induced Ligand Dehydrogenation of a Planar Bis-µ-Chloronickel (I) Dimer Featuring an NHC Ligand,"Inorg. Chem. 2005, 44, 3774-3776.
Mercer, G. J.; Sturdy, M.; Jensen, D. R.; Sigman, M. S. "Intermolecular Reductive Coupling of Hindered N-aryl Imines Towards the Modular Synthesis of Chiral N-Heterocyclic Carbenes,"Tetrahedron2005, 61, 6418-6424.
Schultz, M. J.; Hamilton, S. S.; Jensen, D. R.; Sigman, M. S. "Development and Comparison of Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols,"J. Org. Chem.2005, 70, 3343-3352.


Sigman, M. S.; Schultz, M. J. "The Renaissance of Palladium(II)-Catalyzed Oxidation Chemistry,"Org. Biomol. Chem.2004, 2, 2551-2554 (invited contribution).


Jensen, D. R.; Schultz, M. J.; Mueller, J. A.; Sigman, M. S. "Well-Defined Complex for Palladium-Catalyzed Aerobic Oxidation of Alcohols: Design, Synthesis, and Mechanistic Considerations,"Angew. Chem. Int. Ed. 2003, 42. 3810-3813.
Mandal, S. K. Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. "Scope of Enantioselective Palladium(II)-Catalyzed Aerobic Alcohol Oxidations Using (-)-Sparteine,"J. Org. Chem.2003, 68, 4600-4603.
Dible, B. R.; Sigman, M. S. "Unusual Reactivity of Molecular Oxygen with ?-Allylnickel(N-Heterocyclic Carbene) Chloride Complexes," J. Am. Chem. Soc.2003, 125, 872-873; An Editors' Choice in Science2003, 299, 313.


Schultz, M. J.; Park, C. C.; Sigman, M. S. "A Convenient Pd-Catalyzed Aerobic Oxidation of Alcohols at Room Temperature,"Chem. Commun. 2002, 3034-3035.
Sigman, M. S.; Jensen, D. J.; Rajaram, S. "Enantioselective Oxidations Using Molecular Oxygen," Curr. Opin. Drug Discovery & Development, 2002, 5, 860-869 (invited contribution).
Rajaram, S.; Sigman, M. S. "Modular Synthesis of Amine-Functionalized Oxazolines,"Org. Lett.2002, 4, 3399-3401.
Mueller, J. A.; Jensen, D. R.; Sigman, M. S. "Dual Role of (-)-Sparteine in the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols,"J. Am. Chem. Soc.2002, 124, 8202-8203.


Jensen, D. R.; Pugsley, J. S.; Sigman, M. S. "Palladium-Catalyzed Enantioselective Oxidations of Alcohols Using Molecular Oxygen,"J. Am. Chem. Soc.2001, 123, 7475-7476; Science Concentrate in Chem & Eng. News 2001, 79 (21), 40; Highlighted in Chemtracts by Kenneth M Nicholas Chemtracts 2001, 14, 654-658.


Sigman, M. S.; Vachal, P.; Jacobsen E. N. "A General Catalyst for the Asymmetric Strecker Reaction"Angew. Chem. Int. Ed.2000, 39, 1279-1281.
Sigman, M. S.; Jacobsen, E. N. "Enantioselective Addition of Hydrogen Cyanide to Imines Catalyzed by a (salen)-Al Complex,"J. Am. Chem. Soc.1998, 120, 5315-5316.
Sigman, M. S.; Fatland, A. W.; Eaton, B. E. "Cobalt-Catalyzed Cyclotrimerization of Alkynes in Aqueous Solution,"J. Am. Chem. Soc.1998, 120, 5130-5131.
Sigman, M. S.; Eaton, B. E. "Iron Carbonyl Mediated [4 + 1] Cycloaddition of Diallenes and Carbon Monoxide,"J. Am. Chem. Soc.1996, 118 , 11783-11788.
Sigman, M. S.; Eaton, B. E.; Heise, J. D.; Kubiak, C. P. "Low Temperature Study of the Catalytic Iron Mediated [4 + 1] Cyclization of Allenyl Ketones with Carbon Monoxide,"Organometallics, 1996, 15, 2829-2832.
Sigman, M. S.; Eaton, B. E. "Addition of Primary Amines to Conjugated Allenyl Aldehydes and Ketones,"Tetrahedron Lett.1993, 34, 5367-5368.
Sigman, M. S.; Kerr, C. E.; Eaton, B. E. "Catalytic Iron-Mediated Carbon-Oxygen and Carbon-Carbon Bond Formation in [4 + 1] Assembly of Alkylidenebutenolides,"J. Am. Chem. Soc.1993, 115, 7545-7546.
Last Updated: 9/11/17