个人简介

Education B.S., Lebanon Valley College, 1998 (Carl T. Wigal) Ph.D., University of Michigan 2003 (William H. Pearson) Postdoctoral work, Stanford University (Barry M. Trost) AWARDS AND DISTINCTIONS University Term Professorship Award, 2016-2019 NIH Postdoctoral Fellow, Stanford University, 2003-2006 Eastman Kodak Fellow, University of Michigan, 2002-2003 ACS Division of Organic Chemistry Fellow, 2001-2002 Eastman Kodak Fellow, University of Michigan, 1999-2001 Aaron Aponick was born in Atlantic City, New Jersey in 1976 and grew up in Harrisburg, Pennsylvania. He became interested in organic chemistry at Lebanon Valley College where he studied reactions of quinones with organometallics under the guidance of the late Carl Wigal. After obtaining a B.S. in 1998 he moved to the University of Michigan and joined the research group of Will Pearson. At UM, where he was an Eastman Kodak Fellow and an American Chemical Society, Division of Organic Chemistry Fellow (sponsored by the Schering-Plough Research Institute), his interests in the chemistry of imines, the synthesis of alkaloids, and catalytic enantioselective reactions developed. In 2003, he was awarded a Ph.D. and moved to Stanford University where he worked with Barry Trost as a National Institutes of Health Postdoctoral Fellow. In July 2006, he became an Assistant Professor of Chemistry at the University of Florida and was promoted to Associate Professor in 2013 and Full Professor in 2020.

研究领域

Organic

Research in our lab is directed at the development of new synthetic methodologies to address difficulties in target-oriented synthesis. To control specificity, nature has evolved enzymes that perform chemical reactions with exquisite chemo- diastereo- and enantioselectivity. Our goal is to develop new small molecule catalysts that exhibit synthetically useful levels of selectivity in new chemical transformations. The significance of this work lies in its application to synthesis. Particular attention is given to bioactive natural products with interesting molecular architecture, wherein the objective is to develop efficient synthetic strategies that facilitate extensive structural modifications to probe biological activity. Students in our group will be exposed to the full repertoire of reactions and learn the analytical skills to plan, execute and optimize reaction sequences. Ligand Development We have developed a new concept for increasing the barrier to rotation in biaryls whereby the chiral ground-state conformation is stabilized by π-stacking interactions. This strategy was successfully applied to the design of StackPhos, a new chiral biaryl P,N-ligand incorporating a 5-membered electron-rich heteroaromatic. The ligand is straightforward to prepare and has been demonstrated to be a superb catalyst for the enantioselective A3-coupling and quinoline alkynylation reactions. More importantly, this design concept should be broadly applicable and enable a new class of 5-membered heteroaromatic biaryls to be prepared as catalysts for a range of reactions. Gold Catalysis Density functional calculations and experiment were used to examine the mechanism, reactivity, and origin of chirality transfer in monophosphine Au-catalyzed monoallylic diol cyclization reactions. The lowest energy pathway for cyclization involves a two-step sequence that begins with intramolecular C–O bond formation by anti-addition of the non-allylic hydroxyl group to the Au-coordinated alkene followed by concerted hydrogen transfer/anti-elimination to liberate water. Concerted SN2′-type transition states were found to be significantly higher in energy.

近期论文

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Dahiya, G; Abboud, K. A.; Aponick, A. “Tuning StackPhim Ligands: Applications in Enantioselective Borylation and Alkynylation” Synthesis 2022, ASAP. DOi Liu, J.; Laguna, E. M.; Mangadan, A. R. K.; Kang, K.; Aponick, A. “The Enantioselective Intermolecular Seagusa Allylation” ACS Catal. 2021, 11, 14842 DOi Mangadan, A. R. K.; Liu, J.; Aponick, A. “Enantioselective Lactonization by π-Acid-Catalyzed Allylic Substitution: A Complement to π-Allylmetal Chemistry” Angew. Chem. Int. Ed. 2021, 60, 22224. DOi Dahiya, G.; Pappoppula, M.; Aponick, A. “Configuration sampling with five-membered atropsiomeric P,N- ligands” Angew. Chem. Int. Ed. 2021, 60, 19604. DOi Manda, J. N.; Markovic, M.; Zimmermann, E. M.; Ben-Shabat, S.; Dahan, A.; Aponick, A. “Phospholipid Cyclosporine Prodrugs Targeted at Inflammatory Bowel Disease (IBD) Treatment: Design, Synthesis, and in Vitro Validation” ChemMedChem 2020, 15, 1639. DOi Markovic, M.; Ben-Shabat, S.; Aponick, A.; Zimmermann, E. M.; Dahan, A.; "Lipids and Lipid-Processing Pathways in Drug Delivery and Therapeutics" Int. J. Mol. Sci. 2020, 21, 3248. DOi Mishra, S.; Aponick, A. “Lactone Synthesis by Enantioselective Orthogonal Tandem Catalysis”. Angew. Chem., Int. Ed. 2019, 58, 9485. DOi DeRatt L. G.; Pappoppula, M.; Aponick, A. “A Facile Enantioselective Alkynylation of Chromones”. Angew. Chem., Int. Ed. 2019, 58, 8416. DOi Liu, J.; Mishra, S.; Aponick, A. “Enol Acetates: Versatile Substrates for the Enantioselective. Intermolecular Tsuji Allylation” J. Am. Chem. Soc. 2018, 140, 16152. DOi Markovic, M.; Ben-Shabat, S.; Keinan, S.; Aponick, A; Zimmermann, E. M.; Dahan, A. “Lipid Prodrug. Approach for Improved Oral Drug Delivery and Therapy” Med. Res. Rev. 2018, 39, 579. DOi Markovic, M.; Ben-Shabat, S.; Keinan, S.; Aponick, A; Zimmermann, E. M.; Dahan, A. “Prospects and. Challenges of Phospholipid-Based Prodrug” Pharmaceutics 2018, 10, 210. DOi Liu, J.; Miotto, R. J.; Segard, J.; Erb, A. M.; Aponick, A. “Catalytic Dehydrative Lactonization of Allylic. Alcohols” Org. Lett. 2018, 20, 3034. DOi Dahan, A.; Markovic, M.; Keinan, S.; Kurnikov, I.; Aponick, A.; Zimmermann, E.M.; Ben-Shabat, S. "Computational modeling and in-vitro/in-silico correlation of phospholipid-based prodrugs for targeted. drug delivery in inflammatory bowel disease" J. Comput. Aided Mol. Des. 2017, 31, 1021. DOI Dahan, A.; Markovic, M.; Epstein, S.; Cohen, N.; Zimmerman, E.; Aponick, A.; Ben-Shabat, S.. “Phospholipid-drug conjugates as a novel oral drug targeting approach for the treatment of inflammatory. bowel disease” Eur. J. Pharm. Sci. 2017, 108, 78. DOI Mishra, S.; Liu, J.; Aponick, A. “Enantioselective Alkyne Conjugate Addition Enabled by Readily Tuned. Atropisomeric P,N-Ligands” J. Am. Chem. Soc. 2017, 139, 3352. DOI Paioti, P.H.S.; Abboud, K. A.; Aponick, A. “Incorporation of Axial Chirality into Phosphino-Imidazoline. Ligands for Enantioselective Catalysis” ACS Catal., 2017, 7, 2133. DOI Dahan, A.; Ben-Shabat, S.; Cohen, N.; Keinan, S.; Kurnikov, I.; Aponick, A.; Zimmerman, E. M. “Phospholipid-based prodrugs for drug targeting in inflammatory bowel disease: Computational optimization and in-vitro correlation” Current Topics in Medicinal Chemistry, 2016,16, 2543. DOI Paioti, P.H.S.; Abboud, K. A.; Aponick, A. “Catalytic Enantioselective Synthesis of Amino Skipped Diynes ”J. Am. Chem. Soc. 2016,138, 2150. DOI Silva J. O.; Angnes, R. A.; Silva, V. H. M. ; Servilha, B. M.; Adeel, M.; Braga, A. A. C.; Aponick, A.;. Correia C. R. D. “Intermolecular Non-Covalent Hydroxy-Directed Enantioselective Heck Desymmetrization of Cyclopentenol: Computationally-driven Synthesis of Highly Functionalized cis-4-Aryl-Cyclopentenol Scaffolds”J. Org. Chem. 2016, 81, 2010. DOI Goodwin, J. A.; Ballesteros C. F.; Aponick, A. “Diastereoselective Synthesis of Protected 1,3-Diols by. Catalytic Diol Relocation” Org. Lett. 2015, 17, 5574. DOI Pappoppula, M.; Aponick, A. “Enantioselective Total Synthesis of (-)-Martinellic Acid”. Angew. Chem., Int. Ed. 2015, 54, 15827. DOI Pappoppula, M.; Cardoso, F. S. P.; Garrett, B. O.; Aponick, A. “Enantioselective Cu-Catalyzed. Quinoline Alkynylation” Angew. Chem., Int. Ed. 2015, 54, 15202. DOI Butler, B.B., Jr.; Aponick, A.; Acortatarin A "Spiroketalization Methods and Synthesis. In Strategies and Tactics In Organic Synthesis" Michael Harmata, Ed.; Elsevier: Amsterdam, 2015, 11, 1.DOI Goodwin, J. A.; Aponick, A. “Regioselectivity in the Au-catalyzed hydration and hydroalkoxylation of alkynes” Chem. Commun., 2015, 51, 8730. DOI Butler, B. B.; Manda J. N.; Aponick, A. “Synthesis of the Spirastrellolide A, B/C Spiroketal: Enabling Solutions for Problematic Au(I)-Catalyzed Spiroketalizations” Org. Lett., 2015, 17, 1902. DOI Borrero, N. V.; DeRatt L. G.; Abboud, K. A.; Aponick, A. “Tandem Gold-Catalyzed Dehydrative. Cyclization/Diels–Alder Reactions: Facile Access to Indolocarbazole Alkaloids”. Org. Lett., 2015, 17,1754. DOI Paioti, P.H.S.; Aponick, A. “Progress in Au-Catalyzed Dehydrative Transformations of Unsaturated. Alcohols” Top. Curr. Chem. 2014, 357, 63. DOI Paioti P. H. S.; Ketcham, J. M.; Aponick, A. “Controlling Regiochemistry in the Gold-Catalyzed. Synthesis of Unsaturated Spiroketals” Org. Lett., 2014, 16, 5320. DOI Kahali, B.; Marquez, S. B.; Thompson, K. W.; Yu, J.; Gramling, S. J. B.; Lu, L.; Aponick, A.; Reisman,. D. “Flavonoids from each of the six structural groups reactivate BRM, a possible cofactor for thee. anticancer effects of flavonoids” Carcinogenesis 2014, 35, 2183. DOI Cardoso, F. S. P.; Abboud, K. A.; Aponick, A. “Design, Preparation, and Implementation of an. Imidazole-Based Chiral Biaryl P,N-Ligand for Asymmetric Catalysis” J. Am. Chem. Soc. 2013,135, Ketcham, J. M.; Cardoso, F. S. P.; Biannic, B.; Aponick, A. “Nitrogen Nucleophiles in Au-Catalyzed. Dehydrative Cyclization Reactions” Isr. J. Chem. 2013,53, 923. DOI Ghebreghiorgis, T.; Kirk, B. H.; Aponick, A.; Ess, D. H. “Multiple Mechanisms in Pd(II)-Catalyzed SN2'. Reactions of Allylic Alcohols” J. Org. Chem. 2013, 78, 7664. DOI Palmes, J. A.; Paioti, P. H. S.; de Souza, L. P.; Aponick, A. “Pd(II)-Catalyzed Spiroketalization of. Ketoallylic Diols” Chem. Eur. J. 2013, 19, 11613. DOI Cardoso, F. S. P.; Aponick, A. “1,2-Divinylethylene carbonate (mixture of DL- and meso-isomers)” e-EROS 2013. DOI Ketcham, J. M.; Aponick, A. “Synthesis of Saturated Heterocycles via Metal-catalyzed Allylic Alkylation. Reactions” Top. Heterocycl. Chem. 2013, 32, 157. DOI Ketcham, J. M.; Biannic, B.; Aponick, A. “The Tandem Intermolecular Hydroalkoxylation/Claisen. Rearrangment” Chem. Commun. 2013, 49, 4157. Palmes, J. A.; Aponick, A. “Strategies for Spiroketal Synthesis Based on Transition-Metal Catalysis”. Synthesis 2012, 44, 3699. DOI Borrero, N. V.; Aponick, A. “Total Synthesis of Acortatarin A using a Pd(II)-Catalyzed Spiroketalization. Strategy” J. Org. Chem. 2012, 77, 8410. DOI Ghebreghiorgis, T.; Biannic, B.; Kirk, B. H.; Ess, D. H.; Aponick, A. “The Importance of Hydrogen. Bonding to Stereoselectivity and Catalyst Turnover in Gold-Catalyzed Cyclization of Monoallylic. Diols” J. Am. Chem. Soc. 2012, 134, 16307. DOI Biannic, B.; Aponick, A. “Gold-Catalyzed Dehydrative Transformations of Unsaturated Alcohols” Eur. J. Org. Chem. 2011, 6605. Biannic, B.; Ghebreghiorgis, T.; Aponick, A. “A comparative study of the Au-catalyzed cyclization of hydroxy-substituted allylic alcohols and ethers” Beilstein J. Org. Chem. 2011, 7, 802. DOI Chojnacka, K,; Santoro, S.; Awartani, R.; Richards, N. G. J.; Himo, F.; Aponick, A. “Synthetic Studies on the Solanacol ABC Ring System by Cation-Initiated Cascade Cyclization: Implications for. Strigolactone Biosynthesis” Org. Biomol. Chem. 2011, 9, 5350. DOI Aponick, A; Biannic, B.; “Chirality Transfer in Au-Catalyzed Cyclization Reactions of Monoallylic Diols:. Selective Access to Specific Enatiomers Based on Olefin Geometry” Org. Lett. 2011, 13, 1330. DOI Aponick, A; Biannic, B.; Jong, M. R. “A highly adaptable catalyst system for the synthesis of substituted chromenes” Chem. Commun. 2010, 46, 6849. DOI Aponick, A; Li, C.-Y.; Malinge, J.; Marques, E.F.; “An Extremely Facile Synthesis of Furans, Pyrroles,. and Thiopenes by the Dehydrative Cyclization of Propargyl Alcohols” Org. Lett., 2009, 11, 4624. DOI Aponick, A; Li, C.-Y.; Palmes, J. A.; “Au-catalyzed cyclization of Monopropargylic Triols: An Expedient. Synthesis of Monounsaturated Spiroketals.” Org. Lett., 2009, 11, 121. DOI Aponick, A.; Biannic, B.; “Gold Catalyzed Dehydrative Cyclization of Allylic Diols”. Synthesis, 2008, 20, 3356. DOI Aponick, A.; Dietz, A. L.; Pearson, W. H.; “2-(3-Pyrrolin-1-yl)-1,4-naphthoquinones: Photoactivated. Alkylating Agents” Eur. J. Org. Chem., 2008, 25. DOI Aponick, A.; Li, C.-Y.; Biannic, B.; “Au-Catalyzed Cyclization of Monoallylic Diols” . Org. Lett., 2008, 10, 669. DOI Trost, B.M.; Aponick, A.; Stanzl, B.N. “A Convergent Pd-Catalyzed Asymmetric Allylic Alkylation of. dl- and meso-Divinylethylene Carbonate: Enantioselective Synthesis of (+)-Australine Hydrochloride”. Chem.- Eur. J. 2007, 13, 9547. DOI Trost, B.M.; Machacek, M.R.; Aponick, A. “Predicting the Stereochemistry of DPPBA Based Palladium-. Catalyzed Asymmetric Allylic Alkylation Reactions: A Working Model”. Acc. Chem. Res., 2006, 39, 747. DOI Pearson, W.H.; Aponick, A.; Dietz, A.L. “Synthesis of N,N-Bis(3-butenyl)amines from 2-Azaallyl. Dication Synthetic Equivalents and Conversion to 2,3,6,7-Tetrahydroazepines by Ring-Closing Metathesis” J. Org. Chem. 2006, 71, 3533. DOI Pearson, W.H.; Aponick, A. “Formal Synthesis of Aspidosperma Alkaloids via the Intramolecular [3+2]. Cycloaddition of 2-Azapentadienyllithiums” Org. Lett. 2006, 8, 1661. DOI Trost, B.M.; Aponick, A. “Palladium-Catalyzed Asymmetric Allylic Alkyation of meso- and dl-1,2-. Divinylethylene Carbonate” J. Am. Chem. Soc. 2006, 128, 3931. DOI Aponick, A.; Buzdygon, R.S.; Tomko, R.J.; Fazal, A.N.; Shughart, E.L.; McMaster, D.M.; Myers, M.C.; Pitcock, W.H.; Wigal, C.T. “Regioselective Organocadmium Alkylations of Substituted Quinones” J. Org. Chem. 2002, 67, 242. DOI Pearson, W.H.; Stevens, E.P.; Aponick, A. “Studies on the Asymmetric Cycloaddition of 2-Azaallyl. Anions with Alkenes” Tetrahedron Lett. 2001, 42, 7361. DOI Pearson, W.H.; Aponick, A. “Double Allylation Reactions of (2-Azaallyl)stannanes: Synthesis of. N,N-Bis(3-butenyl)amines and Their Conversion to 2,3,6,7-Tetrahydroazepines via Ring-Closing Metathesis” Org. Lett. 2001, 3, 1327. DOI Aponick, A.; McKinley, J.; Raber, J.C.; Wigal, C.T. “Quinone Alkylation Using Organocadmium. Reagents: A General Synthesis of Quinols” J. Org. Chem. 1998, 63, 2676. DOI Aponick, A.; Marchozzi, E.; Johnston, C.; Wigal, C.T. “Determining the Authenticity of Gemstones. Using Raman Spectroscopy” J. Chem. Ed. 1998, 75, 465. DOI McKinley, J.; Aponick, A.; Raber, J.C.; Fritz, C.; Montgomery, D.; Wigal, C.T. “Reactions of. Alkyllithium and Grignard Reagents with Benzoquinone: Evidence for an Electron-Transfer Mechanism” J. Org. Chem. 1997, 62, 4874. DOI