Publications
2011
(79) Sigman, M.S.; Werner, E.W. "Imparting Catalyst-Control upon Classical Palladium-Catalyzed Alkenyl C-H Bond Functionalization" Acc. Chem. Res., 2011, ASAP.
(78) Harper, K.C.; Sigman, M.S. "Three-Dimensional Correlation of Steric and Electronic Free Energy Relationships Guides Asymmetric Propargylation" Science., 2011, 333, 1875-1878.
(77) 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.
(76) 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.
(75) Podhajsky, S. M.; Iwai, Y.; Cook-Sneathen, A.; Sigman, M. S. "Asymmetric Palladium-Catalyzed Hydroarylation of Styrenes and Dienes" Tetrahedron, 2011, 67, 4435-4441.
(74) 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.
(73) Pathak, T. J.; Sigman, M. S. "Palladium-Catalyzed Hydro-functionalization of Vinyl Phenol Derivatives with Heteroaromatics" Org. Lett., 2011, 13, 2774-2777.
(72) 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.
(71) 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.
(70) 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.
(69) 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.
2010
(68) 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.
(67) 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.
(66) 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.
(65) 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.
(64) 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.
(63) 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.
(62) 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.
(61) 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.
(60) 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.
2009
(59) 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.
(58) 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.
(57) 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
(56) 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
(55) 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.
(54) 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.
(53) 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.
(52) 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.
2008
(51) Jensen, K. H.; Sigman, M. S. "Mechanistic Approaches to Palladium-Catalyzed Alkene Difunctionalization Reactions," Org. Biomol. Chem. 2008, 8, 4083-4088.
(50) 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.
(49) 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.
2007
(48) 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.
(47) Podhajsky, S. M.; Sigman, M. S. "Coupling a Pd-Catalyzed Alcohol Oxidation to Olefin Functionalization: Hydrohalogenation/Hydroalkoxylation of Styrenes,” Organometallics 2007, 26, 5680-5686.
(46) Jensen, K. H. ; Sigman, M. S. "Systematically Probing the Effect of Catalyst Acidity in a Hydrogen-Bond-Catalyzed Enantioselective Reaction,” Angew. Chem., Int. Ed. 2007, 46, 4748-4750.
(45) Zhang, Y.; Sigman, M. S. "Palladium(II)-Catalyzed Enantioselective Aerobic Dialkoxylation of 2-Propenyl Phenols: A Pronounced Effect of Copper Additives on Enantioselectivity,” J. Am. Chem. Soc. 2007, 129, 3076-3077.
(44) Miller, J. J.; Sigman, M. S. “Design and Synthesis of Modular Oxazoline Ligands for the Enantioselective Chromium-Catalyzed Addition of Allyl Bromide to Ketones,” J. Am. Chem. Soc. 2007, 129, 2752-2753.
(43) Cornell, C. N.; Sigman, M. S. “Recent Progress in Wacker Oxidations: Moving Toward Molecular Oxygen as the Sole Oxidant,” Inorg. Chem. 2007, 46, 1903-1909.
2006
(42) 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.
(41) Schultz, M. J.; Sigman, M. S. "Recent Advances in Homogeneous Transition Metal-Catalyzed Aerobic Alcohol Oxidations," Tetrahedron 2006, 62, 8227-8241.
(40) Dible, B. R.; Sigman, M. S. "Steric Effects in the Aerobic Oxidation of Π-Allylnickel(II) Complexes with N-Heterocyclic Carbenes," Inorg. Chem. 2006, 45, 8430-8441.
(39) Zhang, Y.; Sigman, M. S. “Development of a General PdII-Catalyzed Intermolecular Hydroalkoxylation Reaction of Vinylphenols by Using a Sacrificial Alcohol as the Hydride Source,” Org. Lett. 2006, 8, 5557-5560.
(38) Cornell, C. N.; Sigman, M. S. “Discovery of a Practical Direct O2-Coupled Wacker Oxidation using Pd[(-)-Sparteine]Cl2,” Org. Lett. 2006, 8, 4117-4120.
(37) Sigman, M. S.; Jensen, D. R. "Ligand-Modulated Palladium-Catalyzed Aerobic Alcohol Oxidations," Acc. Chem. Res. 2006, 39, 221-229.
(36) 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.
(35) 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.
(34) 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.
2005
(33) Rajaram, S.; Sigman, M. S. "Design of Hydrogen Bond Catalysts Based on a Modular Oxazoline Template: Application to an Enantioselective Hetero Diels-Alder Reaction," Org. Lett. 2005, 7, 5473-5475.
(32) 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.
(31) Lee, J.-Y.; Miller, J. J.; Hamilton, S. S.; Sigman, M. S. "Stereochemical Diversity in Chiral Ligand Design: Discovery and Optimization of Catalysts for the Enantioselective Addition of Allylic Halides to Aldehydes," Org. Lett. 2005, 7, 1837-1839.
(30) 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.
(29) 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.
(28) Cornell, C. N.; Sigman, M. S. "Discovery of and Mechanistic Insight into a Ligand-Modulated Palladium Catalyzed Wacker Oxidation of Styrenes using TBHP," J. Am. Chem. Soc. 2005, 127, 2796-2797.
(27) 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," Tetrahedron 2005, 61, 6418-6424.
(26) 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.
2004
(25) Sigman, M. S.; Schultz, M. J. "The Renaissance of Palladium(II)-Catalyzed Oxidation Chemistry," Org. Biomol. Chem. 2004, 2, 2551-2554 (invited contribution).
(24) Mueller, J. A.; Goller, C. P. , Sigman, M. S. "Elucidating the Significance of β-Hydride Elimination and the Dynamic Role of Acid/Base Chemistry in a Palladium-Catalyzed Aerobic Oxidation of Alcohols," J. Am. Chem. Soc. 2004, 126, 9724-9734.
2003
(23) 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.
(22) Mandal, S. K.; Sigman, M. S. "Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Alcohols Using an Achiral Exogenous Base," J. Org. Chem., 2003, 68, 7535-7537.
(21) 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.
(20) Mueller, J. A.; Sigman, M. S. "Mechanistic Investigations of the Palladium-Catalyzed Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Using (-)-Sparteine," J. Am. Chem. Soc. 2003, 125, 7005-7013.
(19) Mercer, G. J.; Sigman, M. S. "Diastereoselective Synthesis of Piperazines by Manganese-Mediated Reductive Cyclization," Org. Lett. 2003, 5, 1591-1594.
(18) Jensen, D. R.; Sigman, M. S. "Palladium-Catalysts for Aerobic Oxidative Kinetic Resolution of Secondary Alcohols Based on Mechanistic Insight," Org. Lett. 2003, 5, 63-65.
(17) Dible, B. R.; Sigman, M. S. "Unusual Reactivity of Molecular Oxygen with π-Allylnickel(N-Heterocyclic Carbene) Chloride Complexes," J. Am. Chem. Soc. 2003, 125, 872-873; An Editors’ Choice in Science 2003, 299, 313.
2002
(16) 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.
(15) Sigman, M. S.; Jensen, D. J.; Rajaram, S. "Enantioselective Oxidations Using Molecular Oxygen," Curr. Opin. Drug Discovery & Development, 2002, 5, 860-869 (invited contribution).
(14) Rajaram, S.; Sigman, M. S. "Modular Synthesis of Amine-Functionalized Oxazolines," Org. Lett. 2002, 4, 3399-3401.
(13) 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.
2001
(12) 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.
2000 and earlier
(11) Sigman, M. S.; Vachal, P.; Jacobsen E. N. "A General Catalyst for the Asymmetric Strecker Reaction" Angew. Chem. Int. Ed. 2000, 39, 1279-1281.
(10) 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.
(9) 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.
(8) Sigman, M. S.; Jacobsen, E. N. "Schiff Base Catalysts for the Asymmetric Strecker Reaction Identified and Optimized by Parallel Synthetic Libraries," J. Am. Chem. Soc. 1998, 120, 4901-4902.
(7) 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.
(6) 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.
(5) Netzel, T. L.; Zhao, M.; Kambiz N. K.; Headrick, J.; Sigman, M. S.; Eaton, B. E. "Photophysics of 2'-Deoxyuridine (dU) Nucleosides Covalently Substituted With Either 1-Pyrenyl or 1-Pyrenoyl: Direct Evidence for Pyrene-to-Nucleoside Charge-Transfer Emission in 5-(1-Pyrenyl)-dU," J. Am. Chem. Soc. 1995, 117, 9119-9128.
(4) Sigman, M. S.; Eaton, B. E. "The First Iron-Mediated Catalytic Carbon-Nitrogen Bond Formation: [4 + 1] Cycloaddition of Allenyl Imines and Carbon Monoxide," J. Org. Chem. 1994, 59, 7488-7491.
(3) Sigman, M. S.; Eaton, B. E. "Addition of Primary Amines to Conjugated Allenyl Aldehydes and Ketones," Tetrahedron Lett. 1993, 34, 5367-5368.
(2) 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.
(1) Wright, M. E.; Sigman, M. S. "Organometallic Nonlinear Optical Polymers. 3. Copolymerization of Bridged Bis(ferrocenyl) and Bis(cyanoacetate) Monomers Via the Knoevenagel Condensation," Macromolecules 1992, 25, 6055-6058.
