Synthetic Organic Chemistry: Natural Product Synthesis, New Chemical Methods, and Function/Discovery-Oriented Synthesis
Publications
(108) Z. D. Stempel, H. S. Radomska, C. C. Coss, G. C.Micalizio ” Function-Oriented Synthesis of Pentacyclic Triterpenoids and Discovery of an ent-Estrane as a Natural Product-Inspired Androgen Receptor Antagonist” Org. Lett. 2024, 26, accepted.
(107) T. J. Fazekus and G. C. Micalizio “Progress Toward the Asymmetric De Novo Synthesis of Limonoids” Org. Lett. 2024, 26, 1073–1076.
(106) L. E. Markham, T. Koelblen, H. R. Chobanian, A. Viacava Follis, T. P. Burris, G. C. Micalizio “From Functional Fatty Acids to Potent and Selective Natural Product-Inspired Mimetics via Conformational Profiling” ACS Central Science, 2024, 10, 477–486.
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Recent Patent Publications:
(105) C19 Scaffold and Steroids and Methods of Use and Manufacture Thereof (US2021 10323998A1).
(104) Steroids and Methods of Manufacture (US2023 0018615A1).
(103) Chiral Oligomeric Pentenoate Amide as Bio-Oligomer Mimetics (US9963481B2),
(102) Glucocorticoid Receptor Modulators (US2023 0212215A1),
(101) Liver X Receptor Modulators (WO2022 241404A1),
(100) Androgen Receptor Modulators (WO2021 188415A1 ; WO2022198191A1),
(99) Methods for Assembly of Tetracyclic Compounds by Stereoselective C9–C10 Bond Formation (US2023 0151053A1; US20210188898A1),
(98) Therapeutic Uses of Glucocorticoids with Anabolic Effects in Skeletal Muscle (US2023 0263808A1 ; WO2022 081725A1),
(97) Methods for Convenient Asymmetric Synthesis of C9-Substituted Steroid-like Compounds (WO2022 198224A1);
(96) Stereoselective C9–C10 Bond Formation (WO2022 226473A1).
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(95) J. M. Nicholson, G. C. Micalizio, “Asymmetric Total Syntheses of Euphol and Tirucallol” Org. Lett. 2023, 25, 5687–5691.
(94) A. R. Bucknam, G. C. Micalizio, “Progress Toward the Asymmetric de Novo Synthesis of Lanostanes: A Counter Biomimetic Cucurbitane-to-Lanostane Type Transformation” Tetrahedron (virtual issue in honor of Professor John L. Wood), 2023, 141, 133498.
(93) H. T. Wai, G. C. Micalizio, ” Toward the Asymmetric De Novo Synthesis of Lanostanes: Construction of 7,11-dideoxy-D5-lucidadone H” J. Org. Chem. 2022, 87, 14975-14979. (92) A. B. Millham, G. C. Micalizio, “Toward the Asymmetric Synthesis of Cardenolides and Related Steroidal Systems: syn-SN2′ of Organometallics with C14–C17 Vinyelepoxides” Org. Lett. 2022, 24, 7058-7061.(91) H.T. Wai, T. Koelblen, M. E. Hayes, T. P. Burris, G. C. Micalizio, “Progress Toward the De Novo Asymmetric Synthesis of Euphanes” Org. Lett. 2022, 24, 3686-3690.(90) A. R. Bucknam, G. C. Micalizio “Asymmetric De Novo Synthesis of a Cucurbitane Triterpenoid: Total Synthesis of Octanorcucurbitacin B” J. Am. Chem. Soc. 2022, 144, 8493-8497.(89) J. M. Nicholson, A. B. Millham, A. R. Bucknam, L. E. Markham, X. E. Sailors, G. C. Micalizio, “A General Enantioselective and Stereochemically Divergent Four-Stage Approach to Fused Tetracyclic Terpenoid Systems” J. Org. Chem. 2022, 87, 3352-3362.(88) L. E. Markham, J. D. Tolbert, F. J. Kull, C. R. Midgett, G. C. Micalizio, “An Enantiodefined Conformationally Constrained Fatty Acid Mimetic and Potent Inhibitor of ToxT” ACS Med. Chem. Lett. 2021, 12, 1493-1497.
(87) Z. A. Shalit, L. Valdes, W. S. Kim, G. C. Micalizio, “From an ent-Estrane, Through a nat-Androstane, to the Total Synthesis of the Marine-Derived Δ8,9-Pregnene (+)-03219A” Org. Lett.2021, 23, 2248-2252.(86) A. B. Millham, C. P. Bhatt, G. C. Micalizio, “From Metallacycle-Mediated Annulative Cross-Coupling to Steroidal Tetracycles Through Intramolecular C9–C10 Bond Formation” Org. Lett.2020, 22, 6595-6599.
(85) K. Du, M. J. Kier, Z. D. Stempel, V. Jeso, A. Rheingold, G. C. Micalizio “Synthesis of Anhydroryanodol” J. Am. Chem. Soc.2020, 142, 12937-12941 (84) R. Karmakar, A. Rheingold, G. C. Micalizio “Studies Targeting Ryanodol Result in an Annulation Reaction for the Synthesis of a Variety of Fused Carbocycles” Org. Lett.2019, 21, 6126-6129.(83) R. M. Leon, D. Ravi, C. del Genio, A. L. Rheingold, A. B. Gaur, G. C. Micalizio “Synthesis of C14-Desmethylene Corialactone D and the Discovery of Inhibitors of Nerve Growth Factor-Mediated Neurite Outgrowth” Org. Lett. 2019, 21, 3193-3197.(82) W. S. Kim, Z. A. Shalit, S. Nguyen, E. Schoepke, A. Eastman, T. P. Burris, A. B. Gaur, G. C. Micalizio “A Synthesis Strategy for Tetracyclic Terpenoids Leads to Agonists of ERβ” Nature Communications,2019, 10, article #2448 (DOI: 10.1038/s41467-019-10415-6). For press release, see Dartmouth and AAAS EurekAlert.(81) A. B. Millham, M. J. Kier, R. M. Leon, R. Karmakar, Z. D. Stempel, G. C. Micalizio “A Complementary Process to Pauson–Khand-type Annulation Reactions for the Construction of Fully Substituted Cyclopentenones” Org. Lett.,2019, 21, 567-570.(80) K. Du, M. J. Kier, A. L. Rheingold, G. C. Micalizio “Toward the Total Synthesis of Ryanodol via Oxidative Alkyne–1,3-Diketone Annulation: Construction of a Ryanoid Tetracycle” Org. Lett. 2018, 20, 6457-6461.(79) H.T. Wai, K. Du, J. Anesini, W. S. Kim, A. Eastman, G. C. Micalizio “Synthesis and Discovery of Estra-1,3,5(10),6,8-pentene-2,16α-diol” Org. Lett. 2018, 20, 6220-6224.(78) Z. A. Shalit, G. C. Micalizio “A Highly Chemo-, Regio-, and Stereoselective Metallacycle-Mediated Annulation Between a Conjugated Enyne and an Ene-Diyne” (invited – special issue honoring Professor Gordon Gribble) Arkivoc, 2018, 132-138.
(77) W. S. Kim, K. Du, R. P. Hughes, G. C. Micalizio “Synthetic nat– or ent-Steroids in as Few as Five Chemical Steps from Epichlorohydrin” Nat. Chem. 2018, 10, 70-77.(76) N. F. O’Rourke, A Mu, H. N. Higgs, A. Eastman, and G. C. Micalizio “Function-Oriented Studies Targeting Pectenotoxin 2: Synthesis of the GH-Ring System and a Structurally Simplified Macrolactone” Org. Lett. 2017, 19, 5154-5157.(75) M. J. Kier, R. M. Leon, N. F. O’Rourke, A. L. Rheingold, G. C. Micalizio “Synthesis of Highly Oxygenated Carbocycles by Stereoselective Coupling of Alkynes to 1,3- and 1,4-Dicarbonyl Systems” J. Am. Chem. Soc. 2017, 139, 12374-12377.(74) X. Cheng, G. C. Micalizio “The Application of Metallacycle-mediated Cross-coupling to the Synthesis of Neurotrophic seco-Prezizaane Natural Products” invited Chapter in Strategies and Tactics in Organic Synthesis vol. 13, 2017, 35-54.(73) H. Mizoguchi, G. C. Micalizio “The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry” Invited Review dedicated to Professors Stuart L. Schreiber and K. C. Nicolaou in celebration of their receipt of the 2016 Wolf Prize in Chemistry: Isr. J. Chem. 2017, 57, 228-238.
(72) H. Mizoguchi, G. C. Micalizio “Synthesis of Angularly Substituted trans-fused Decalins by a Metallacycle-Mediated Annulative Cross-Coupling Cascade” Angew. Chem. Int. Ed. 2016, 55, 13099-13103.(71) N. F. O’Rourke, M. J. Kier, G. C. Micalizio “Metallacycle-Mediated Cross-Coupling in Natural Product Synthesis” (invited Report) Tetrahedron 2016, 72, 7093-7123.(70) J. S. Cassidy, H. Mizoguchi, G. C. Micalizio “Acceleration of Metallacycle-mediated Alkyne–Alkyne Cross-coupling with TMSCl” Tetrahedron Lett.2016, 57, 3848-3850.(69) C. Aquino, S. N. Greszler, G. C. Micalizio “Synthesis of the Cortistatin Pentacyclic Core by Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling” Org. Lett.2016, 18, 2624-2627.(68) N. F. O’Rourke, G. C. Micalizio “Cyclopropenes in Metallacycle-Mediated Cross-Coupling with Alkynes: Convergent synthesis of highly substituted vinylcyclopropanes” Org. Lett.2016, 18, 1250-1253.(67) X. Cheng, G. C. Micalizio “Synthesis of Neurotrophic Seco-prezizaane Sesquiterpenes (1R,10S)-2-oxo-3,4-dehydroneomajucin, (2S)-hydroxy-3,4-dehydroneomajucin, and (–)-jiadifenin” J. Am. Chem. Soc.2016, 138, 1150-1153.(66) H. Mizoguchi, G. C. Micalizio “Synthesis of Highly Functionalized Decalins via Metallacycle-Mediated Cross-Coupling” J. Am. Chem. Soc.2015, 137, 6624-6628.(65)G. C. Micalizio, S. Hale “Reaction Design, Discovery, and Development as a Foundation to Function-Oriented Synthesis” Acc. Chem. Res. (invited), 2015, 48, 663-673.(64) W. S. Kim, C. Aquino, Mizoguchi, H.; G. C. Micalizio “LiOOt-Bu as a Terminal Oxidant in a Titanium-Mediated [2+2+2] Reaction Cascade” Symposium-in-Print (invited), Tetrahedron Lett.2015, 56, 3557-3559.(63) X. Cheng, G. C. Micalizio “An Annulation Reaction for the Synthesis of Cross-Conjugated Triene-containing Hydroindanes from Acyclic Precursors” Org. Lett.2014, 16, 5144-5147.(62) V. Jeso, C. Aquino, X. Cheng, H. Mizoguchi, M. Nakashige, G. C. Micalizio “Synthesis of Angularly Substituted Trans-fused Hydroindanes by Convergent Coupling of Acyclic Precursors” J. Am. Chem. Soc.2014, 136, 8209-8212.(61) Comprehensive Organic Synthesis II. G. C. Micalizio “Early Transition Metal-Mediated Reductive Coupling Reactions” In: Comprehensive Organic Synthesis, 2nd edition; Gary A. Molander and Paul Knochel (eds.), Oxford: Elsevier; 2014; Vol. 5; pp. 1660-1737.
(60) X. Li, V. Jeso, S. Heyward, G. S. Walker, R. Sharma, G. C. Micalizio, M. D. Cameron, “Characterization of T-5 N-oxide Formation as the First Highly Selective Measure of CYP3A5 Activity” Drug Metabolism and Disposition, 2014, 42, 334-342.
(59) D. P. Canterbury, O. Kubo, K. N. Scott, J. L. Cleveland, G. C. Micalizio, “Synthesis of C11-Desmethoxy Soraphen A1a: A natural product analog that inhibits acetyl-CoA carboxylase” ACS Med. Chem. Lett. 2013, 4, 1244-1248.(58) D. Yang, G. C. Micalizio, “Stereochemical Lability of Azatitanacyclopropanes and an Efficient Dynamic Kinetic Reoslution in Reductive Cross-Coupling Reactions with Allylic Alcohols” Chem. Commun.2013, 49, 8857-8859.
(57) V. Jeso, S. Iqbal, P. Hernandez, M. D. Cameron, H. Park, P. V. LoGrasso, G. C. Micalizio “Synthesis of Benzoquinone Ansamycin-Inspired Macrocyclic Lactams from Shikimic Acid” Angew. Chem. Int. Ed.2013, 52, 4800-4804.(56) V. Jeso, C. Yang, M. D. Cameron, J. L. Cleveland, G. C. Micalizio “Synthesis and Structure–Activity Relationships of Lehualide B – A Marine-derived Natural Product with Potent Anti-Multiple Myeloma Activity” ACS Chemical Biology, 2013, 8, 1241-1252.(55) V. Jeso, G. C. Micalizio “Relay catalysis at a boron centre” Nature (News and Views) 2013, 494, 179-181.
(54) M. Sarkar, B. D. Pascal, C. Steckler, C. Aquino, G. C. Micalizio, T. Kodadek, M. J. Chalmers “Decoding Split-and-Pool Combinatorial Libraries with Electron Transfer Dissociation Tandem Mass Spectrometry” J. Am. Soc. Mass Spec.2013, 24, 1026-1036.
(53) O. Kubo, D. P. Canterbury, G. C. Micalizio “Synthesis of the C1-C26 Hexacyclic Subunit of Pectenotoxin 2” Org. Lett.2012, 14, 5748-5751.(52) D. Yang, G. C. Micalizio “Synthesis of Alkaloid (–)-205B via Stereoselective Reductive Cross-Coupling and Intramolecular [3+2] Cycloaddition” J. Am. Chem. Soc.2012, 134, 15237-15240.(51) P. S. Diez, G. C. Micalizio “Convergent Synthesis of Deoxypropionates” Angew. Chem. Int. Ed.2012, 51, 5152-5156.(50) S. Greszler, H. A. Reichard, G. C. Micalizio “Asymmetric Synthesis of Dihydroindanes by Convergent Alkoxide-Directed Metallacycle-Mediated Bond Formation” J. Am. Chem. Soc.2012, 134, 2766-2774.(49) M. Z. Chen, G. C. Micalizio “Three-Component Coupling Sequence for the Regiospecific Synthesis of Substituted Pyridines” J. Am. Chem. Soc.2012, 134, 1352-1356.(48) C. Aquino, M. Sarkar, M. J. Chalmers, K. Mendez, T. Kodadek, G. C. Micalizio “A Biomimetic Polyketide-Inspired Approach to Small Molecule Ligand Discovery” Nature Chem.2012, 4, 99-104.(47) Science of Synthesis – Knowledge Updates 2012/4: G. C. Micalizio “Titanium-Mediated Reductive Cross-Coupling (Intermolecular Metallacycle-Mediated C–C Bond Formation)” Science of Synthesis, 2012, 33-97.
(46) D. Yang, G. C. Micalizio, “Convergent and Stereodivergent Synthesis of Complex 1-Aza-7-Oxabicyclo[2.2.1]heptanes” J. Am. Chem. Soc.2011, 133, 9216-9219.(45) M. A. Tarselli, K. M. Raehal, A. K. Brasher, C. Groer, M. D. Cameron, L. M. Bohn, G. C. Micalizio, “Synthesis of Conolidine, a Potent Non-Opioid Analgesic for Tonic and Persistent Pain” Nature Chem.2011, 3, 449-453.(44) V. Jeso, L. Cherry, T. K. Macklin, S. C. Pan, P. V. LoGrasso, G. C. Micalizio “Convergent Synthesis and Discovery of a Natural Product-Inspired Paralog-Selective Hsp90 Inhibitor” Org. Lett. 2011, 13, 5108-5111.(43) D. P. Canterbury, G. C. Micalizio “Convergent Route to the CDEF Tetracycle of Pectenotoxin-2” Org. Lett.2011, 13, 2384-2387.(42) H. A. Reichard, G. C. Micalizio “Metallacycle-Mediated Cross-Coupling with Substituted and Electronically Unactivated Alkenes” Chem. Sci. 2011, 2, 573-589.(41) D. Yang, J. K. Belardi, G. C. Micalizio “Generation of quaternary centers by reductive cross-coupling: shifting of regioselectivity in a subset of allylic alcohol-based coupling reactions” Tetrahedron Lett.2011, 52, 2144-2147.(40) M. Z. Chen, M. McLaughlin, M. Takahashi, M. A. Tarselli, D. Yang, S. Umemura, G. C. Micalizio “Preparation of Stereodefined Homoallylic Amines from the Reductive Cross-Coupling of Allylic Alcohols with Imines” J. Org. Chem., 2010, 75, 8048-8059.(39) V. Jeso, G. C. Micalizio “Total Synthesis of Lehualide B by Allylic Alcohol–Alkyne Reductive Cross-Coupling” J. Am. Chem. Soc.2010, 132, 11422-11424.(38) P. S. Diez, G. C. Micalizio “Chemoselective Reductive Cross-Coupling of 1,5-Diene-3-ols with Alkynes: A Facile Entry to Stereodefined Skipped Trienes” J. Am. Chem. Soc.2010, 132, 9576-9578.(37) D. P. Canterbury, G. C. Micalizio “Polyketide Assembly by Alkene–Alkyne Reductive Cross-Coupling: Spiroketals Through the Union of Homoallylic Alcohols” J. Am. Chem. Soc.2010, 132, 7602-7604.(36) T. K. Macklin, G. C. Micalizio “Convergent and Stereospecific Synthesis of Skipped Polyenes and Polyunsaturated Fatty Acids” Nature Chem.2010, 2, 638-643.(35) M. Takahashi, G. C. Micalizio “Concerning the Potential Reversibility of Carbometalation in Akoxide-directed Ti(Oi-Pr)4-mediated Reductive Cross-Coupling of Homoallylic Alcohols with Aromatic Imines” Chem. Commun. 2010, 46, 3336-3338.
(34) A. U. Barlan, G. C. Micalizio “The Regio- and Stereochemical Course of Reductive Cross-Coupling Reactions Between 1,3-Disubstituted Allenes and Vinylsilanes: Synthesis of Z-Dienes” Tetrahedron, 2010, 66, 4775-4783.(33) H. A. Reichard, M. McLaughlin, M. Z. Chen, G. C. Micalizio “Regioselective Reductive Cross-Coupling Reactions of Unsymmetrical Alkynes” Eur. J. Org. Chem. 2010, 391-409.
(32) D. Yang, G. G. Micalizio “A Convergent Stereoselective Synthesis of Quinolizidines and Indolizidines: Chemoselective Coupling of 2-Hydroxymethyl Substituted Allylic Silanes with Imines” J. Am. Chem. Soc.2009, 131, 17548-17549.(31) S. Umemura, M. McLaughlin, G. C. Micalizio “Convergent Synthesis of Stereodefined Exo-alkylidene-ϒ-Lactams from β-Halo Allylic Alcohols” Org. Lett.2009, 11, 5402-5405.(30) M. Z. Chen, G. C. Micalizio “Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis” Org. Lett.2009, 11, 4982-4985.(29) M. A. Tarselli, G. C. Micalizio “Aliphatic Imines in Titanium-Mediated Reductive Cross-Coupling: Unique Reactivity of Ti(Oi-Pr)4/n-BuLi” Org. Lett. 2009, 11, 4596-4599.(28) L. J. Perez, H. L. Shimp, G. C. Micalizio “Stereoselective Synthesis of Trisubstituted (E,E)-1,3-Dienes by the Site-Selective Reductive Cross-Coupling of Internal Alkynes with Terminal Alkynes: A New Fragment Coupling Reaction for Natural Product Synthesis” J. Org. Chem., 2009, 74, 7211-7219.(27) H. L. Shimp, G. C. Micalizio “A Formal Total Synthesis of Dictyostatin” Tetrahedron, 2009, 65, 5908-5915.(26) M. Takahashi, M. McLaughlin, G. C. Micalizio “Complex Allylation by the Direct Cross-Coupling of Imines with Unactivated Allylic Alcohols” Angew. Chem. Int. Ed. 2009, 48, 3648-3652.(25) T. K. Macklin, G. C. Micalizio “Total Synthesis and Structure Elucidation of (+)-Phorbasin C” J. Am. Chem. Soc. 2009, 131, 1392-1393.(24) J. K. Belardi, G. C. Micalizio “Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement” J. Am. Chem. Soc.2008, 130, 16870-16872.(23) H. A. Reichard, J. C. Rieger, G. C. Micalizio “Total Synthesis of Callystatin A by Titanium-mediated Reductive Alkyne–Alkyne Cross-Coupling” Angew. Chem. Int. Ed. 2008, 47, 7837-7840.(22) J. K. Belardi, G. C. Micalizio “Total Synthesis of Macbecin I” Angew. Chem. Int. Ed. 2008, 47, 4005-4008.(21) H. L. Shimp, A. Hare, M. McLaughlin, G. C. Micalizio “Allene-alkyne cross-coupling for stereoselective synthesis of substituted 1,4-dienes and cross-conjugated trienes” Tetrahedron2008, 64, 3437-3445 and 6831-6837.(20) M. McLaughlin, H. L. Shimp, R. Navarro, G. C. Micalizio “Regio- and Stereoselective Direct Cross-Coupling of Imines with Allenic Alcohols” Synlett2008, 735-738.(19) L. J. Perez, G. C. Micalizio “Titanium-Mediated Fragment Union Processes in Complex Molecule Synthesis: Development of a Branched Reaction Pathway of High Step Economy for the Synthesis of Complex and Diverse Polyketides” Synthesis 2008, 627-648.
(18) F. Kolundzic, G. C. Micalizio “Synthesis of Substituted 1,4-Dienes by Direct Alkylation of Allylic Alcohols” J. Am. Chem. Soc. 2007, 129, 15112-15113.(17) M. Takahashi, G. C. Micalizio “Regio- and Stereoselective Cross Coupling of Substituted Olefins and Imines. A Convergent Stereoselective Synthesis of Saturated 1,5-Aminoalcohols and Substituted Piperidines” J. Am. Chem. Soc. 2007, 129, 7514-7516.(16) H. L. Shimp, G. C. Micalizio “An Alkoxide-Directed Alkyne–Allene Cross-Coupling for Stereoselective Synthesis of 1,4-Dienes” Chem. Commun.2007, 4531-4533.(15) M. McLaughlin, M. Takahashi, G. C. Micalizio “An Alkoxide Directed Intermolecular [2+2+1] Annulation: A Three-Component Coupling Reaction for the Synthesis of Tetrasubstituted α,β-Unsaturated γ-Lactams” Angew. Chem. Int. Ed. 2007, 46, 3912-3914.(14) H. A. Reichard, G. C. Micalizio, “A Site- and Stereoselective Intermolecular Alkene–Alkyne Coupling Process” Angew. Chem. Int. Ed. 2007, 46, 1440-1443.(13) J. K. Belardi, G. C. Micalizio “Studies on the Syntheses of Benzoquinone Ansamycin Antibiotics. Syntheses of the C(5)-C(15) Subunits of Macbecin I, Geldanamycin and Herbimycin A” Org. Lett.2006, 8, 2409-2412. (12) A. B. Bahadoor, G. C. Micalizio “Studies in Macrolide Antibiotic Synthesis: The Role of Tethered Alkoxides in Titanium Alkoxide-mediated Regioselective Reductive Coupling Reactions” Org. Lett.2006, 8, 1181-1184.(11) J. Ryan and G. C. Micalizio “An Alkoxide-directed Carbometalation of Internal Alkynes” J. Am. Chem. Soc. 2006, 128, 2764-2765.(10) H. L. Shimp and G. C. Micalizio “Group 4 Metals in Polyketide Synthesis: A Convergent Strategy for the Synthesis of Polypropionate-Derived (E,E)-Trisubstituted 1,3-Dienes” Org. Lett. 2005, 7, 5111-5114.(9) A. B. Bahadoor, A. Flyer, G. C. Micalizio “A Pentenyl Dianion-based Strategy for Convergent Synthesis of Ene-1,5-diols” J. Am. Chem. Soc. 2005, 127, 3694-3695.
Publications as a Graduate Student and Postdoctoral Fellow:
(8) J.-N. Heo, G. C. Micalizio, W. R. Roush, “Enantio- and Diastereoselective Synthesis of Cyclic b-Hydroxy Allylsilanes via Sequential Aldehyde g-Silylallylboration and Ring Closing Metathesis Reactions” Org. Lett.2003, 5, 1693.
(7) G. C. Micalizio and S. L. Schreiber, “An Alkynylboronic Ester Annulation: Development of Synthetic Methods For Application to Diversity-Oriented Organic Synthesis” Angew. Chem. Int. Ed.2002, 41, 3272.
(6) G. C. Micalizio and S. L. Schreiber, “A Boronic Ester Annulation Strategy for Diversity-Oriented Organic Synthesis” Angew. Chem. Int. Ed. 2002, 41, 152.
(5) G. C. Micalizio and W. R. Roush, “Studies on the Synthesis of Pectenotoxin II: Synthesis of a C(11)-C(26) Fragment Precursor via [3+2]-Annulation Reactions of Chiral Allylsilanes” Org. Lett. 2001, 3, 1949.
(4) W. R. Roush, A. N. Pinchuk, G. C. Micalizio, “[(E)-g-(Dimethylphenylsilyl)-allyl]diisopino-campheylborane: a highly enantioselective reagent for the synthesis of anti-b-hydroxy-allylsilanes” Tetrahedron Lett. 2000, 41, 9413.
(3) G. C. Micalizio, W. R. Roush, and A. N. Pinchuk, “Synthesis of the C(29)-C(45) E-F Bis-Pyran Subunit of Spongistatin 1 (Altohyrtin A)” J. Org. Chem. 2000, 65, 8730.
(2) G. C. Micalizio and W. R. Roush, “A Three-Component Coupling Strategy for Tetrahydrofuran Synthesis: Application of the Diisopropyl Tartrate Modified (E)-g-Dimethylphenylsilyl- allylboronate as an a,g-Allyl Dianion Equivalent” Org. Lett.2000, 2, 461.
(1) G. C. Micalizio and W. R. Roush, “Towards the Synthesis of Spongistatin 1: Diastereoselective Synthesis of the C(36)-C(45) Subunit” Tetrahedron Lett.1999, 40, 3351.
(107) T. J. Fazekus and G. C. Micalizio “Progress Toward the Asymmetric De Novo Synthesis of Limonoids” Org. Lett. 2024, 26, 1073–1076.
(106) L. E. Markham, T. Koelblen, H. R. Chobanian, A. Viacava Follis, T. P. Burris, G. C. Micalizio “From Functional Fatty Acids to Potent and Selective Natural Product-Inspired Mimetics via Conformational Profiling” ACS Central Science, 2024, 10, 477–486.
(94) A. R. Bucknam, G. C. Micalizio, “Progress Toward the Asymmetric de Novo Synthesis of Lanostanes: A Counter Biomimetic Cucurbitane-to-Lanostane Type Transformation” Tetrahedron (virtual issue in honor of Professor John L. Wood), 2023, 141, 133498.
(93) H. T. Wai, G. C. Micalizio, ” Toward the Asymmetric De Novo Synthesis of Lanostanes: Construction of 7,11-dideoxy-D5-lucidadone H” J. Org. Chem. 2022, 87, 14975-14979. 
(92) A. B. Millham, G. C. Micalizio, “Toward the Asymmetric Synthesis of Cardenolides and Related Steroidal Systems: syn-SN2′ of Organometallics with C14–C17 Vinyelepoxides” Org. Lett. 2022, 24, 7058-7061.
(91) H.T. Wai, T. Koelblen, M. E. Hayes, T. P. Burris, G. C. Micalizio, “Progress Toward the De Novo Asymmetric Synthesis of Euphanes” Org. Lett. 2022, 24, 3686-3690.
(90) A. R. Bucknam, G. C. Micalizio “Asymmetric De Novo Synthesis of a Cucurbitane Triterpenoid: Total Synthesis of Octanorcucurbitacin B” J. Am. Chem. Soc. 2022, 144, 8493-8497.
(89) J. M. Nicholson, A. B. Millham, A. R. Bucknam, L. E. Markham, X. E. Sailors, G. C. Micalizio, “A General Enantioselective and Stereochemically Divergent Four-Stage Approach to Fused Tetracyclic Terpenoid Systems” J. Org. Chem. 2022, 87, 3352-3362.
(88) L. E. Markham, J. D. Tolbert, F. J. Kull, C. R. Midgett, G. C. Micalizio, “An Enantiodefined Conformationally Constrained Fatty Acid Mimetic and Potent Inhibitor of ToxT” ACS Med. Chem. Lett. 2021, 12, 1493-1497.
(87) Z. A. Shalit, L. Valdes, W. S. Kim, G. C. Micalizio, “From an ent-Estrane, Through a nat-Androstane, to the Total Synthesis of the Marine-Derived Δ8,9-Pregnene (+)-03219A” Org. Lett. 2021, 23, 2248-2252.
(86) A. B. Millham, C. P. Bhatt, G. C. Micalizio, “From Metallacycle-Mediated Annulative Cross-Coupling to Steroidal Tetracycles Through Intramolecular C9–C10 Bond Formation” Org. Lett. 2020, 22, 6595-6599.
(85) K. Du, M. J. Kier, Z. D. Stempel, V. Jeso, A. Rheingold, G. C. Micalizio “Synthesis of Anhydroryanodol” J. Am. Chem. Soc. 2020, 142, 12937-12941 
(84) R. Karmakar, A. Rheingold, G. C. Micalizio “Studies Targeting Ryanodol Result in an Annulation Reaction for the Synthesis of a Variety of Fused Carbocycles” Org. Lett. 2019, 21, 6126-6129.
(83) R. M. Leon, D. Ravi, C. del Genio, A. L. Rheingold, A. B. Gaur, G. C. Micalizio “Synthesis of C14-Desmethylene Corialactone D and the Discovery of Inhibitors of Nerve Growth Factor-Mediated Neurite Outgrowth” Org. Lett. 2019, 21, 3193-3197.
(82) W. S. Kim, Z. A. Shalit, S. Nguyen, E. Schoepke, A. Eastman, T. P. Burris, A. B. Gaur, G. C. Micalizio “A Synthesis Strategy for Tetracyclic Terpenoids Leads to Agonists of ERβ” Nature Communications, 2019, 10, article #2448 (DOI: 10.1038/s41467-019-10415-6). For press release, see Dartmouth and AAAS EurekAlert.
(81) A. B. Millham, M. J. Kier, R. M. Leon, R. Karmakar, Z. D. Stempel, G. C. Micalizio “A Complementary Process to Pauson–Khand-type Annulation Reactions for the Construction of Fully Substituted Cyclopentenones” Org. Lett., 2019, 21, 567-570.
(80) K. Du, M. J. Kier, A. L. Rheingold, G. C. Micalizio “Toward the Total Synthesis of Ryanodol via Oxidative Alkyne–1,3-Diketone Annulation: Construction of a Ryanoid Tetracycle” Org. Lett. 2018, 20, 6457-6461.
(79) H.T. Wai, K. Du, J. Anesini, W. S. Kim, A. Eastman, G. C. Micalizio “Synthesis and Discovery of Estra-1,3,5(10),6,8-pentene-2,16α-diol” Org. Lett. 2018, 20, 6220-6224.
(78) Z. A. Shalit, G. C. Micalizio “A Highly Chemo-, Regio-, and Stereoselective Metallacycle-Mediated Annulation Between a Conjugated Enyne and an Ene-Diyne” (invited – special issue honoring Professor Gordon Gribble) Arkivoc, 2018, 132-138.
(77) W. S. Kim, K. Du, R. P. Hughes, G. C. Micalizio “Synthetic nat– or ent-Steroids in as Few as Five Chemical Steps from Epichlorohydrin” Nat. Chem. 2018, 10, 70-77.
(76) N. F. O’Rourke, A Mu, H. N. Higgs, A. Eastman, and G. C. Micalizio “Function-Oriented Studies Targeting Pectenotoxin 2: Synthesis of the GH-Ring System and a Structurally Simplified Macrolactone” Org. Lett. 2017, 19, 5154-5157.
(75) M. J. Kier, R. M. Leon, N. F. O’Rourke, A. L. Rheingold, G. C. Micalizio “Synthesis of Highly Oxygenated Carbocycles by Stereoselective Coupling of Alkynes to 1,3- and 1,4-Dicarbonyl Systems” J. Am. Chem. Soc. 2017, 139, 12374-12377.
(74) X. Cheng, G. C. Micalizio “The Application of Metallacycle-mediated Cross-coupling to the Synthesis of Neurotrophic seco-Prezizaane Natural Products” invited Chapter in Strategies and Tactics in Organic Synthesis vol. 13, 2017, 35-54.
(73) H. Mizoguchi, G. C. Micalizio “The Development of Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling Chemistry” Invited Review dedicated to Professors Stuart L. Schreiber and K. C. Nicolaou in celebration of their receipt of the 2016 Wolf Prize in Chemistry: Isr. J. Chem. 2017, 57, 228-238.
(72) H. Mizoguchi, G. C. Micalizio “Synthesis of Angularly Substituted trans-fused Decalins by a Metallacycle-Mediated Annulative Cross-Coupling Cascade” Angew. Chem. Int. Ed. 2016, 55, 13099-13103.
(71) N. F. O’Rourke, M. J. Kier, G. C. Micalizio “Metallacycle-Mediated Cross-Coupling in Natural Product Synthesis” (invited Report) Tetrahedron 2016, 72, 7093-7123.
(70) J. S. Cassidy, H. Mizoguchi, G. C. Micalizio “Acceleration of Metallacycle-mediated Alkyne–Alkyne Cross-coupling with TMSCl” Tetrahedron Lett. 2016, 57, 3848-3850.
(69) C. Aquino, S. N. Greszler, G. C. Micalizio “Synthesis of the Cortistatin Pentacyclic Core by Alkoxide-Directed Metallacycle-Mediated Annulative Cross-Coupling” Org. Lett. 2016, 18, 2624-2627.
(68) N. F. O’Rourke, G. C. Micalizio “Cyclopropenes in Metallacycle-Mediated Cross-Coupling with Alkynes: Convergent synthesis of highly substituted vinylcyclopropanes” Org. Lett. 2016, 18, 1250-1253.
(67) X. Cheng, G. C. Micalizio “Synthesis of Neurotrophic Seco-prezizaane Sesquiterpenes (1R,10S)-2-oxo-3,4-dehydroneomajucin, (2S)-hydroxy-3,4-dehydroneomajucin, and (–)-jiadifenin” J. Am. Chem. Soc. 2016, 138, 1150-1153.
(66) H. Mizoguchi, G. C. Micalizio “Synthesis of Highly Functionalized Decalins via Metallacycle-Mediated Cross-Coupling” J. Am. Chem. Soc. 2015, 137, 6624-6628.
(65) G. C. Micalizio, S. Hale “Reaction Design, Discovery, and Development as a Foundation to Function-Oriented Synthesis” Acc. Chem. Res. (invited), 2015, 48, 663-673.
(64) W. S. Kim, C. Aquino, Mizoguchi, H.; G. C. Micalizio “LiOOt-Bu as a Terminal Oxidant in a Titanium-Mediated [2+2+2] Reaction Cascade” Symposium-in-Print (invited), Tetrahedron Lett. 2015, 56, 3557-3559.
(63) X. Cheng, G. C. Micalizio “An Annulation Reaction for the Synthesis of Cross-Conjugated Triene-containing Hydroindanes from Acyclic Precursors” Org. Lett. 2014, 16, 5144-5147.
(62) V. Jeso, C. Aquino, X. Cheng, H. Mizoguchi, M. Nakashige, G. C. Micalizio “Synthesis of Angularly Substituted Trans-fused Hydroindanes by Convergent Coupling of Acyclic Precursors” J. Am. Chem. Soc. 2014, 136, 8209-8212.
(61) Comprehensive Organic Synthesis II. G. C. Micalizio “Early Transition Metal-Mediated Reductive Coupling Reactions” In: Comprehensive Organic Synthesis, 2nd edition; Gary A. Molander and Paul Knochel (eds.), Oxford: Elsevier; 2014; Vol. 5; pp. 1660-1737.
(60) X. Li, V. Jeso, S. Heyward, G. S. Walker, R. Sharma, G. C. Micalizio, M. D. Cameron, “Characterization of T-5 N-oxide Formation as the First Highly Selective Measure of CYP3A5 Activity” Drug Metabolism and Disposition, 2014, 42, 334-342.
(59) D. P. Canterbury, O. Kubo, K. N. Scott, J. L. Cleveland, G. C. Micalizio, “Synthesis of C11-Desmethoxy Soraphen A1a: A natural product analog that inhibits acetyl-CoA carboxylase” ACS Med. Chem. Lett. 2013, 4, 1244-1248.
(58) D. Yang, G. C. Micalizio, “Stereochemical Lability of Azatitanacyclopropanes and an Efficient Dynamic Kinetic Reoslution in Reductive Cross-Coupling Reactions with Allylic Alcohols” Chem. Commun. 2013, 49, 8857-8859.
(56) V. Jeso, C. Yang, M. D. Cameron, J. L. Cleveland, G. C. Micalizio “Synthesis and Structure–Activity Relationships of Lehualide B – A Marine-derived Natural Product with Potent Anti-Multiple Myeloma Activity” ACS Chemical Biology, 2013, 8, 1241-1252.
(55) V. Jeso, G. C. Micalizio “Relay catalysis at a boron centre” Nature (News and Views) 2013, 494, 179-181.
(54) M. Sarkar, B. D. Pascal, C. Steckler, C. Aquino, G. C. Micalizio, T. Kodadek, M. J. Chalmers “Decoding Split-and-Pool Combinatorial Libraries with Electron Transfer Dissociation Tandem Mass Spectrometry” J. Am. Soc. Mass Spec. 2013, 24, 1026-1036.
(53) O. Kubo, D. P. Canterbury, G. C. Micalizio “Synthesis of the C1-C26 Hexacyclic Subunit of Pectenotoxin 2” Org. Lett. 2012, 14, 5748-5751.
(52) D. Yang, G. C. Micalizio “Synthesis of Alkaloid (–)-205B via Stereoselective Reductive Cross-Coupling and Intramolecular [3+2] Cycloaddition” J. Am. Chem. Soc. 2012, 134, 15237-15240.
(51) P. S. Diez, G. C. Micalizio “Convergent Synthesis of Deoxypropionates” Angew. Chem. Int. Ed. 2012, 51, 5152-5156.
(50) S. Greszler, H. A. Reichard, G. C. Micalizio “Asymmetric Synthesis of Dihydroindanes by Convergent Alkoxide-Directed Metallacycle-Mediated Bond Formation” J. Am. Chem. Soc. 2012, 134, 2766-2774.
(49) M. Z. Chen, G. C. Micalizio “Three-Component Coupling Sequence for the Regiospecific Synthesis of Substituted Pyridines” J. Am. Chem. Soc. 2012, 134, 1352-1356.
(48) C. Aquino, M. Sarkar, M. J. Chalmers, K. Mendez, T. Kodadek, G. C. Micalizio “A Biomimetic Polyketide-Inspired Approach to Small Molecule Ligand Discovery” Nature Chem. 2012, 4, 99-104.
(47) Science of Synthesis – Knowledge Updates 2012/4: G. C. Micalizio “Titanium-Mediated Reductive Cross-Coupling (Intermolecular Metallacycle-Mediated C–C Bond Formation)” Science of Synthesis, 2012, 33-97.
(46) D. Yang, G. C. Micalizio, “Convergent and Stereodivergent Synthesis of Complex 1-Aza-7-Oxabicyclo[2.2.1]heptanes” J. Am. Chem. Soc. 2011, 133, 9216-9219.
(45) M. A. Tarselli, K. M. Raehal, A. K. Brasher, C. Groer, M. D. Cameron, L. M. Bohn, G. C. Micalizio, “Synthesis of Conolidine, a Potent Non-Opioid Analgesic for Tonic and Persistent Pain” Nature Chem. 2011, 3, 449-453.
(44) V. Jeso, L. Cherry, T. K. Macklin, S. C. Pan, P. V. LoGrasso, G. C. Micalizio “Convergent Synthesis and Discovery of a Natural Product-Inspired Paralog-Selective Hsp90 Inhibitor” Org. Lett. 2011, 13, 5108-5111.
(43) D. P. Canterbury, G. C. Micalizio “Convergent Route to the CDEF Tetracycle of Pectenotoxin-2” Org. Lett. 2011, 13, 2384-2387.
(42) H. A. Reichard, G. C. Micalizio “Metallacycle-Mediated Cross-Coupling with Substituted and Electronically Unactivated Alkenes” Chem. Sci. 2011, 2, 573-589.
(41) D. Yang, J. K. Belardi, G. C. Micalizio “Generation of quaternary centers by reductive cross-coupling: shifting of regioselectivity in a subset of allylic alcohol-based coupling reactions” Tetrahedron Lett. 2011, 52, 2144-2147.
(40) M. Z. Chen, M. McLaughlin, M. Takahashi, M. A. Tarselli, D. Yang, S. Umemura, G. C. Micalizio “Preparation of Stereodefined Homoallylic Amines from the Reductive Cross-Coupling of Allylic Alcohols with Imines” J. Org. Chem., 2010, 75, 8048-8059.
(39) V. Jeso, G. C. Micalizio “Total Synthesis of Lehualide B by Allylic Alcohol–Alkyne Reductive Cross-Coupling” J. Am. Chem. Soc. 2010, 132, 11422-11424.
(38) P. S. Diez, G. C. Micalizio “Chemoselective Reductive Cross-Coupling of 1,5-Diene-3-ols with Alkynes: A Facile Entry to Stereodefined Skipped Trienes” J. Am. Chem. Soc. 2010, 132, 9576-9578.
(37) D. P. Canterbury, G. C. Micalizio “Polyketide Assembly by Alkene–Alkyne Reductive Cross-Coupling: Spiroketals Through the Union of Homoallylic Alcohols” J. Am. Chem. Soc. 2010, 132, 7602-7604.
(36) T. K. Macklin, G. C. Micalizio “Convergent and Stereospecific Synthesis of Skipped Polyenes and Polyunsaturated Fatty Acids” Nature Chem. 2010, 2, 638-643.
(35) M. Takahashi, G. C. Micalizio “Concerning the Potential Reversibility of Carbometalation in Akoxide-directed Ti(Oi-Pr)4-mediated Reductive Cross-Coupling of Homoallylic Alcohols with Aromatic Imines” Chem. Commun. 2010, 46, 3336-3338.
(33) H. A. Reichard, M. McLaughlin, M. Z. Chen, G. C. Micalizio “Regioselective Reductive Cross-Coupling Reactions of Unsymmetrical Alkynes” Eur. J. Org. Chem. 2010, 391-409.
(31) S. Umemura, M. McLaughlin, G. C. Micalizio “Convergent Synthesis of Stereodefined Exo-alkylidene-ϒ-Lactams from β-Halo Allylic Alcohols” Org. Lett. 2009, 11, 5402-5405.
(30) M. Z. Chen, G. C. Micalizio “Convergent Synthesis of Piperidines by the Union of Conjugated Alkynes with Imines: A Unique Regioselective Bond Construction for Heterocycle Synthesis” Org. Lett. 2009, 11, 4982-4985.
(29) M. A. Tarselli, G. C. Micalizio “Aliphatic Imines in Titanium-Mediated Reductive Cross-Coupling: Unique Reactivity of Ti(Oi-Pr)4/n-BuLi” Org. Lett. 2009, 11, 4596-4599.
(28) L. J. Perez, H. L. Shimp, G. C. Micalizio “Stereoselective Synthesis of Trisubstituted (E,E)-1,3-Dienes by the Site-Selective Reductive Cross-Coupling of Internal Alkynes with Terminal Alkynes: A New Fragment Coupling Reaction for Natural Product Synthesis” J. Org. Chem., 2009, 74, 7211-7219.
(27) H. L. Shimp, G. C. Micalizio “A Formal Total Synthesis of Dictyostatin” Tetrahedron, 2009, 65, 5908-5915.
(26) M. Takahashi, M. McLaughlin, G. C. Micalizio “Complex Allylation by the Direct Cross-Coupling of Imines with Unactivated Allylic Alcohols” Angew. Chem. Int. Ed. 2009, 48, 3648-3652.
(25) T. K. Macklin, G. C. Micalizio “Total Synthesis and Structure Elucidation of (+)-Phorbasin C” J. Am. Chem. Soc. 2009, 131, 1392-1393.
(24) J. K. Belardi, G. C. Micalizio “Conversion of Allylic Alcohols to Stereodefined Trisubstituted Alkenes: A Complementary Process to the Claisen Rearrangement” J. Am. Chem. Soc. 2008, 130, 16870-16872.
(23) H. A. Reichard, J. C. Rieger, G. C. Micalizio “Total Synthesis of Callystatin A by Titanium-mediated Reductive Alkyne–Alkyne Cross-Coupling” Angew. Chem. Int. Ed. 2008, 47, 7837-7840.
(22) J. K. Belardi, G. C. Micalizio “Total Synthesis of Macbecin I” Angew. Chem. Int. Ed. 2008, 47, 4005-4008.
(21) H. L. Shimp, A. Hare, M. McLaughlin, G. C. Micalizio “Allene-alkyne cross-coupling for stereoselective synthesis of substituted 1,4-dienes and cross-conjugated trienes” Tetrahedron 2008, 64, 3437-3445 and 6831-6837.
(20) M. McLaughlin, H. L. Shimp, R. Navarro, G. C. Micalizio “Regio- and Stereoselective Direct Cross-Coupling of Imines with Allenic Alcohols” Synlett 2008, 735-738.
(19) L. J. Perez, G. C. Micalizio “Titanium-Mediated Fragment Union Processes in Complex Molecule Synthesis: Development of a Branched Reaction Pathway of High Step Economy for the Synthesis of Complex and Diverse Polyketides” Synthesis 2008, 627-648.
(17) M. Takahashi, G. C. Micalizio “Regio- and Stereoselective Cross Coupling of Substituted Olefins and Imines. A Convergent Stereoselective Synthesis of Saturated 1,5-Aminoalcohols and Substituted Piperidines” J. Am. Chem. Soc. 2007, 129, 7514-7516.
(16) H. L. Shimp, G. C. Micalizio “An Alkoxide-Directed Alkyne–Allene Cross-Coupling for Stereoselective Synthesis of 1,4-Dienes” Chem. Commun. 2007, 4531-4533.
(15) M. McLaughlin, M. Takahashi, G. C. Micalizio “An Alkoxide Directed Intermolecular [2+2+1] Annulation: A Three-Component Coupling Reaction for the Synthesis of Tetrasubstituted α,β-Unsaturated γ-Lactams” Angew. Chem. Int. Ed. 2007, 46, 3912-3914.
(14) H. A. Reichard, G. C. Micalizio, “A Site- and Stereoselective Intermolecular Alkene–Alkyne Coupling Process” Angew. Chem. Int. Ed. 2007, 46, 1440-1443.
(13) J. K. Belardi, G. C. Micalizio “Studies on the Syntheses of Benzoquinone Ansamycin Antibiotics. Syntheses of the C(5)-C(15) Subunits of Macbecin I, Geldanamycin and Herbimycin A” Org. Lett. 2006, 8, 2409-2412.
(12) A. B. Bahadoor, G. C. Micalizio “Studies in Macrolide Antibiotic Synthesis: The Role of Tethered Alkoxides in Titanium Alkoxide-mediated Regioselective Reductive Coupling Reactions” Org. Lett. 2006, 8, 1181-1184.
(11) J. Ryan and G. C. Micalizio “An Alkoxide-directed Carbometalation of Internal Alkynes” J. Am. Chem. Soc. 2006, 128, 2764-2765.
(10) H. L. Shimp and G. C. Micalizio “Group 4 Metals in Polyketide Synthesis: A Convergent Strategy for the Synthesis of Polypropionate-Derived (E,E)-Trisubstituted 1,3-Dienes” Org. Lett. 2005, 7, 5111-5114.
(9) A. B. Bahadoor, A. Flyer, G. C. Micalizio “A Pentenyl Dianion-based Strategy for Convergent Synthesis of Ene-1,5-diols” J. Am. Chem. Soc. 2005, 127, 3694-3695.
