Paul E. Floreancig

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Name: Floreancig, Paul; Paul E. Floreancig

Organization: University of Pittsburgh , USA

Department: Department of Chemistry

Title: Professor(PhD)

TOPICS

Organic Chemistry

Chemicals
References

Re2O7-Mediated Dehydrative Cyclization Reactions: Total Synthesis of Herboxidiene and Its 12-Desmethyl Analogue

Co-reporter:Tyler M. Rohrs;Qi Qin; Dr. Paul E. Floreancig

Angewandte Chemie International Edition 2017 Volume 56(Issue 36) pp:10900-10904

Publication Date(Web):2017/08/28

DOI:10.1002/anie.201705924

AbstractRe2O7 catalysis effects efficient and stereoselective dehydrative cyclization reactions from monoallylic diols, with stereocontrol arising from thermodynamic equilibration. This method was applied to a rapid synthesis of the spliceosome inhibitor herboxidiene. The route was also utilized for the synthesis of an analogue that highlights the importance of a single methyl group in biasing the conformation in the acyclic region of the molecule.

Alcohol, Aldehyde, and Ketone Liberation and Intracellular Cargo Release through Peroxide-Mediated α-Boryl Ether Fragmentation

Co-reporter:Ramsey D. Hanna, Yuta Naro, Alexander Deiters, and Paul E. Floreancig

Journal of the American Chemical Society 2016 Volume 138(Issue 40) pp:13353-13360

Publication Date(Web):September 16, 2016

DOI:10.1021/jacs.6b07890

α-Boryl ethers, carbonates, and acetals, readily prepared from the corresponding alcohols that are accessed through ketone diboration, react rapidly with hydrogen peroxide to release alcohols, aldehydes, and ketones through the collapse of hemiacetal intermediates. Experiments with α-boryl acetals containing a latent fluorophore clearly demonstrate that cargo can be released inside cells in the presence of exogenous or endogenous hydrogen peroxide. These experiments show that this protocol can be used for drug activation in an oxidative environment without generating toxic byproducts.

Convergent One-Pot Oxidative [n + 1] Approaches to Spiroacetal Synthesis

Co-reporter:GuangRong Peh and Paul E. Floreancig

Organic Letters 2015 Volume 17(Issue 15) pp:3750-3753

Publication Date(Web):July 21, 2015

DOI:10.1021/acs.orglett.5b01736

Two one-pot oxidative annulative approaches to spiroacetal synthesis are described. One approach uses a Lewis acid mediated Ferrier reaction in the fragment-coupling stage followed by DDQ-promoted oxidative carbon–hydrogen bond cleavage and cyclization. An alternative approach employs a Heck reaction for fragment coupling followed by DDQ-mediated enone formation and cyclization. These strategies provide convergent routes to common subunits in natural products, medicinal agents, and chemical libraries under mild reaction conditions.

Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups

Co-reporter:Youwei Xie ; Paul E. Floreancig

Angewandte Chemie 2014 Volume 126( Issue 19) pp:5026-5029

Publication Date(Web):

DOI:10.1002/ange.201402010

Abstract

Allylic alcohols undergo transposition reactions in the presence of Re₂O₇ whereby the equilibrium can be dictated by trapping one isomer with a pendent electrophile. Additional ionization can occur when the trapping group is an aldehyde or ketone, thus leading to cyclic oxocarbenium ion formation. Terminating the process through bimolecular nucleophilic addition into the intermediate provides a versatile method for the synthesis of diverse oxygen-containing heterocycles. Understanding the relative rates of the steps in the sequence leads to the design of reactions which create multiple stereocenters with good to excellent levels of control.

Spiroacetal Formation through Telescoped Cycloaddition and CarbonHydrogen Bond Functionalization: Total Synthesis of BistramideA

Co-reporter:Xun Han ; Paul E. Floreancig

Angewandte Chemie International Edition 2014 Volume 53( Issue 41) pp:11075-11078

Publication Date(Web):

DOI:10.1002/anie.201406819

Abstract

Spiroacetals can be formed through a one-pot sequence of a hetero-Diels–Alder reaction, an oxidative carbon–hydrogen bond cleavage, and an acid treatment. This convergent approach expedites access to a complex molecular subunit which is present in numerous biologically active structures. The utility of the protocol is demonstrated through its application to a brief synthesis of the actin-binding cytotoxin bistramide A.

Spiroacetal Formation through Telescoped Cycloaddition and CarbonHydrogen Bond Functionalization: Total Synthesis of BistramideA

Co-reporter:Xun Han ; Paul E. Floreancig

Angewandte Chemie 2014 Volume 126( Issue 41) pp:11255-11258

Publication Date(Web):

DOI:10.1002/ange.201406819

Abstract

Heterocycle Synthesis Based on Allylic Alcohol Transposition Using Traceless Trapping Groups

Co-reporter:Youwei Xie ; Paul E. Floreancig

Angewandte Chemie International Edition 2014 Volume 53( Issue 19) pp:4926-4929

Publication Date(Web):

DOI:10.1002/anie.201402010

Abstract

Prins-Type Cyclization Reactions in Natural Product Synthesis

Co-reporter:Xun Han;GuangRong Peh

European Journal of Organic Chemistry 2013 Volume 2013( Issue 7) pp:1193-1208

Publication Date(Web):

DOI:10.1002/ejoc.201201557

Abstract

Prins-type cyclization reactions proceed through the intramolecular addition of a π-nucleophile to an oxocarbenium ion or related species to generate a ring through carbon–carbon bond formation, often with excellent and predictable stereocontrol. The widespread presence of naturally occurring oxygen-containing heterocycles has made these reactions exceedingly valuable for total synthesis efforts. This microreview covers several common variations of Prins-type cyclizations and highlights their applicability to the total synthesis of natural products and analogs.

Bimolecular coupling reactions through oxidatively generated aromatic cations: scope and stereocontrol

Co-reporter:Yubo Cui, Louis A. Villafane, Dane J. Clausen, Paul E. Floreancig

Tetrahedron 2013 69(36) pp: 7618-7626

Publication Date(Web):

DOI:10.1016/j.tet.2013.05.011

Stereocontrolled Cyanohydrin Ether Synthesis through Chiral Brønsted Acid-Mediated Vinyl Ether Hydrocyanation

Co-reporter:Chunliang Lu, Xiaoge Su, and Paul E. Floreancig

The Journal of Organic Chemistry 2013 Volume 78(Issue 18) pp:9366-9376

Publication Date(Web):August 22, 2013

DOI:10.1021/jo4016002

Vinyl ethers can be protonated to generate oxocarbenium ions that react with Me3SiCN to form cyanohydrin alkyl ethers. Reactions that form racemic products proceed efficiently upon conversion of the vinyl ether to an α-chloro ether prior to cyanide addition in a pathway that proceeds through Brønsted acid-mediated chloride ionization. Enantiomerically enriched products can be accessed by directly protonating the vinyl ether with a chiral Brønsted acid to form a chiral ion pair. Me3SiCN acts as the nucleophile and PhOH serves as a stoichiometric proton source in a rare example of asymmetric bimolecular nucleophilic addition into an oxocarbenium ion. Computational studies have provided a model for the interaction between the catalyst and the oxocarbenium ion.

Cascade Approach to Stereoselective Polycyclic Ether Formation: Epoxides as Trapping Agents in the Transposition of Allylic Alcohols

Co-reporter:Youwei Xie ; Paul E. Floreancig

Angewandte Chemie 2013 Volume 125( Issue 2) pp:653-656

Publication Date(Web):

DOI:10.1002/ange.201208132

Cascade Approach to Stereoselective Polycyclic Ether Formation: Epoxides as Trapping Agents in the Transposition of Allylic Alcohols

Co-reporter:Youwei Xie ; Paul E. Floreancig

Angewandte Chemie International Edition 2013 Volume 52( Issue 2) pp:625-628

Publication Date(Web):

DOI:10.1002/anie.201208132

Stereoselective piperidine synthesis through oxidative carbon–hydrogen bond functionalizations of enamides

Co-reporter:Gediminas J. Brizgys, Hyung Hoon Jung and Paul E. Floreancig

Chemical Science 2012 vol. 3(Issue 2) pp:438-442

Publication Date(Web):05 Oct 2011

DOI:10.1039/C1SC00670C

N-Vinyl amides, carbamates, and sulfonamides that contain pendent π-nucleophiles react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form piperidine structures with good to excellent levels of efficiency and stereocontrol. Reactions proceed nearly instantaneously at room temperature. Transition state models show the preferred configuration around the intermediate acyliminium ion and the orientation of the nucleophile.

Synthesis of Sulfur-Containing Heterocycles through Oxidative Carbon–Hydrogen Bond Functionalization

Co-reporter:Yubo Cui and Paul E. Floreancig

Organic Letters 2012 Volume 14(Issue 7) pp:1720-1723

Publication Date(Web):March 15, 2012

DOI:10.1021/ol3002877

Vinyl sulfides react rapidly and efficiently with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form α,β-unsaturated thiocarbenium ions through oxidative carbon–hydrogen bond cleavage. These electrophiles couple with appended π-nucleophiles to yield sulfur-containing heterocycles through carbon–carbon bond formation. Several nucleophiles are compatible with the procedure, and the reactions generally proceed through readily predictable transition states.

Synthesis of Bridged Inside–Outside Bicyclic Ethers through Oxidative Transannular Cyclization Reactions

Co-reporter:Xun Han and Paul E. Floreancig

Organic Letters 2012 Volume 14(Issue 14) pp:3808-3811

Publication Date(Web):July 11, 2012

DOI:10.1021/ol301720u

The classical geometry of the 6-endo transition state for nucleophilic additions into oxocarbenium ions can be perturbed by incorporating the reactive groups into medium-sized rings, leading to the formation of 2,6-trans-dialkyl tetrahydropyrans. The bicyclic products exhibit inside–outside stereoisomerism, as seen in numerous macrolide natural products.

Cyclopropane Compatibility with Oxidative Carbocation Formation: Total Synthesis of Clavosolide A

Co-reporter:GuangRong Peh and Paul E. Floreancig

Organic Letters 2012 Volume 14(Issue 21) pp:5614-5617

Publication Date(Web):October 24, 2012

DOI:10.1021/ol302744t

Cyclopropane-substituted allylic ethers react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form oxocarbenium ions with no competitive ring cleavage. This reaction can be used for the preparation of cyclopropane-substituted tetrahydropyrans. The protocol was used as a key step in the total synthesis of the sponge-derived macrolide clavosolide A.

Versatile approach to α-alkoxy carbamate synthesis and stimulus-responsive alcohol release

Co-reporter:R. Adam Mosey and Paul E. Floreancig

Organic & Biomolecular Chemistry 2012 vol. 10(Issue 39) pp:7980-7985

Publication Date(Web):30 Aug 2012

DOI:10.1039/C2OB26571K

A series of α-alkoxy carbamates that cleave under mild conditions to release alcohols has been synthesized through a multicomponent process. The relationship between structural features in these compounds and the rate of alcohol release in the presence of basic hydrogen peroxide has been studied. The preparation of carbamates that cleave under other conditions has been demonstrated.

Synthesis and Biological Evaluation of Neopeltolide and Analogs

Co-reporter:Yubo Cui, Raghavan Balachandran, Billy W. Day, and Paul E. Floreancig

The Journal of Organic Chemistry 2012 Volume 77(Issue 5) pp:2225-2235

Publication Date(Web):February 13, 2012

DOI:10.1021/jo2023685

The synthesis of neopeltolide analogues that contain variations in the oxazole-containing side chain and in the macrolide core are reported along with the GI50 values for these compounds against MCF-7, HCT-116, and p53 knockout HCT-116 cell lines. Although biological activity is sensitive to changes in the macrocycle and the side chain, several analogues displayed GI50 values of <25 nM. Neopeltolide and several of the more potent analogues were significantly less potent against p53 knockout cells, suggesting that p53 plays an auxiliary role in the activity of these compounds.

Aromatic Cations from Oxidative Carbon–Hydrogen Bond Cleavage in Bimolecular Carbon–Carbon Bond Forming Reactions

Co-reporter:Dane J. Clausen and Paul E. Floreancig

The Journal of Organic Chemistry 2012 Volume 77(Issue 15) pp:6574-6582

Publication Date(Web):July 10, 2012

DOI:10.1021/jo301185h

Chromenes and isochromenes react quickly with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) to form persistent aromatic oxocarbenium ions through oxidative carbon–hydrogen cleavage. This process is tolerant of electron-donating and electron-withdrawing groups on the benzene ring and additional substitution on the pyran ring. A variety of nucleophiles can be added to these cations to generate a diverse set of structures.

Total Synthesis and Biological Evaluation of Pederin, Psymberin, and Highly Potent Analogs

Co-reporter:Shuangyi Wan ; Fanghui Wu ; Jason C. Rech ; Michael E. Green ; Raghavan Balachandran ; W. Seth Horne ; Billy W. Day

Journal of the American Chemical Society 2011 Volume 133(Issue 41) pp:16668-16679

Publication Date(Web):September 8, 2011

DOI:10.1021/ja207331m

The potent cytotoxins pederin and psymberin have been prepared through concise synthetic routes (10 and 14 steps in the longest linear sequences, respectively) that proceed via a late-stage multicomponent approach to construct the N-acyl aminal linkages. This route allowed for the facile preparation of a number of analogs that were designed to explore the importance of the alkoxy group in the N-acyl aminal and functional groups in the two major subunits on biological activity. These analogs, including a pederin/psymberin chimera, were analyzed for their growth inhibitory effects, revealing several new potent cytotoxins and leading to postulates regarding the molecular conformational and hydrogen bonding patterns that are required for biological activity. Second generation analogs have been prepared based on the results of the initial assays and a structure-based model for the binding of these compounds to the ribosome. The growth inhibitory properties of these compounds are reported. These studies show the profound role that organic chemistry in general and specifically late-stage multicomponent reactions can play in the development of unique and potent effectors for biological responses.

Stereoselective heterocycle synthesis through a reversible allylic alcohol transposition and nucleophilic addition sequence

Co-reporter:Youwei Xie and Paul E. Floreancig

Chemical Science 2011 vol. 2(Issue 12) pp:2423-2427

Publication Date(Web):14 Sep 2011

DOI:10.1039/C1SC00570G

The abilities of Re2O7 to promote non-stereoselective allylic alcohol transposition reactions and acetal ionization or enone activation have been coupled for a heterocycle synthesis in which thermodynamics dictate stereochemical outcomes. The stabilities of intermediate allylic cation and oxocarbenium ion intermediates dictate the efficiency of product equilibration. Long range stereoinduction can be observed in the synthesis of spiroketals and spirotricycles through this protocol.

Total Synthesis of Pederin and Analogues

Co-reporter:Dr. Fanghui Wu;Dr. Michael E. Green;Dr. Paul E. Floreancig

Angewandte Chemie 2011 Volume 123( Issue 5) pp:1163-1166

Publication Date(Web):

DOI:10.1002/ange.201006438

Total Synthesis of the Protein Phosphatase 2A Inhibitor Lactodehydrothyrsiferol

Co-reporter:Dane J. Clausen;Dr. Shuangyi Wan ;Dr. Paul E. Floreancig

Angewandte Chemie International Edition 2011 Volume 50( Issue 22) pp:5178-5181

Publication Date(Web):

DOI:10.1002/anie.201007757

Total Synthesis of Pederin and Analogues

Co-reporter:Dr. Fanghui Wu;Dr. Michael E. Green;Dr. Paul E. Floreancig

Angewandte Chemie International Edition 2011 Volume 50( Issue 5) pp:1131-1134

Publication Date(Web):

DOI:10.1002/anie.201006438

Total Synthesis of the Protein Phosphatase 2A Inhibitor Lactodehydrothyrsiferol

Co-reporter:Dane J. Clausen;Dr. Shuangyi Wan ;Dr. Paul E. Floreancig

Angewandte Chemie 2011 Volume 123( Issue 22) pp:5284-5287

Publication Date(Web):

DOI:10.1002/ange.201007757

2,3-Dichloro-5,6-dicyano-1,4-benzoquinone-Catalyzed Reactions Employing MnO2 as a Stoichiometric Oxidant

Co-reporter:Lei Liu and Paul E. Floreancig

Organic Letters 2010 Volume 12(Issue 20) pp:4686-4689

Publication Date(Web):September 23, 2010

DOI:10.1021/ol102078v

Several oxidative reactions can be effected with MnO2 in the presence of substoichiometric quantities of DDQ. These transformations include oxidative cyclization, deprotection, and dehydrogenation reactions. The use of MnO2 as a terminal oxidant for DDQ-mediated reactions is attractive based on economical and environmental factors.

Stereoselective Synthesis of Spirooxindole Amides through Nitrile Hydrozirconation

Co-reporter:Chunliang Lu, Qing Xiao, and Paul E. Floreancig

Organic Letters 2010 Volume 12(Issue 22) pp:5112-5115

Publication Date(Web):October 20, 2010

DOI:10.1021/ol102246d

Spirooxindole amides can be prepared by the intramolecular addition of functionalized indoles into acylimines that are accessed from nitriles by hydrozirconation and acylation. The stereochemical outcome at the quaternary center was controlled by the steric bulk of the substituent at the 2-position of the indole unit. The products are well-suited for diversification to prepare libraries.

Total synthesis of neopeltolide and analogs

Co-reporter:Yubo Cui, Wangyang Tu, Paul E. Floreancig

Tetrahedron 2010 66(26) pp: 4867-4873

Publication Date(Web):

DOI:10.1016/j.tet.2010.03.066

Stereoselective Synthesis of Tertiary Ethers through Geometric Control of Highly Substituted Oxocarbenium Ions

Co-reporter:Lei Liu ;PaulE. Floreancig Dr.

Angewandte Chemie International Edition 2010 Volume 49( Issue 34) pp:5894-5897

Publication Date(Web):

DOI:10.1002/anie.201002281

Structurally and Stereochemically Diverse Tetrahydropyran Synthesis through Oxidative CH Bond Activation

Co-reporter:Lei Liu ;PaulE. Floreancig Dr.

Angewandte Chemie International Edition 2010 Volume 49( Issue 17) pp:3069-3072

Publication Date(Web):

DOI:10.1002/anie.201000033

Structurally and Stereochemically Diverse Tetrahydropyran Synthesis through Oxidative CH Bond Activation

Co-reporter:Lei Liu ;PaulE. Floreancig Dr.

Angewandte Chemie 2010 Volume 122( Issue 17) pp:3133-3136

Publication Date(Web):

DOI:10.1002/ange.201000033

Stereoselective Synthesis of Tertiary Ethers through Geometric Control of Highly Substituted Oxocarbenium Ions

Co-reporter:Lei Liu ;PaulE. Floreancig Dr.

Angewandte Chemie 2010 Volume 122( Issue 34) pp:6030-6033

Publication Date(Web):

DOI:10.1002/ange.201002281

Cyclization Reactions through DDQ-Mediated Vinyl Oxazolidinone Oxidation

Co-reporter:Lei Liu and Paul E. Floreancig

Organic Letters 2009 Volume 11(Issue 14) pp:3152-3155

Publication Date(Web):June 24, 2009

DOI:10.1021/ol901188q

Vinyl oxazolidinones react with DDQ to form α,β-unsaturated acyliminium ions in a new method for forming electrophiles under oxidative conditions. Appended nucleophiles undergo 1,4-addition reactions with these intermediates to form cyclic vinyl oxazolidinones with good levels of diastereocontrol, highlighting a new approach to utilizing oxidative carbon−hydrogen bond functionalization to increase molecular complexity.

Construction of a Bicyclic β-Benzyloxy and β-Hydroxy Amide Library through a Multicomponent Cyclization Reaction

Co-reporter:Li Zhang, Qing Xiao, Chao Ma, Xiang-Qun Xie and Paul E. Floreancig

ACS Combinatorial Science 2009 Volume 11(Issue 4) pp:640

Publication Date(Web):June 8, 2009

DOI:10.1021/cc800200h

In this manuscript, we describe the synthesis of a bicyclic β-benzyloxy and β-hydroxy amide library from cyanohydrin ethers. The benzyloxy amides were prepared through a one-pot sequence of hydrozirconation, acylation, and intramolecular Friedel−Crafts alkylation. Selected benzyl ethers were converted to alcohols by hydrogenolysis in a continuous flow reactor. Chemistry space BCUT metrics and 2D fingerprint similarity calculations showed that these compounds contribute chemical diversity value to existing chemical libraries.

Oxidative Carbocation Formation in Macrocycles: Synthesis of the Neopeltolide Macrocycle

Co-reporter:Wangyang Tu ;PaulE. Floreancig Dr.

Angewandte Chemie 2009 Volume 121( Issue 25) pp:4637-4641

Publication Date(Web):

DOI:10.1002/ange.200901489

Highly Convergent Synthesis of PelurosideA

Co-reporter:PaulE. Floreancig Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 42) pp:7736-7739

Publication Date(Web):

DOI:10.1002/anie.200903480

Oxidative Carbocation Formation in Macrocycles: Synthesis of the Neopeltolide Macrocycle

Co-reporter:Wangyang Tu ;PaulE. Floreancig Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 25) pp:4567-4571

Publication Date(Web):

DOI:10.1002/anie.200901489

Mechanistic analysis of oxidative C–H cleavages using inter- and intramolecular kinetic isotope effects

Co-reporter:Hyung Hoon Jung, Paul E. Floreancig

Tetrahedron 2009 65(52) pp: 10830-10836

Publication Date(Web):

DOI:10.1016/j.tet.2009.10.088

Eine hoch konvergente Synthese von PelurosidA

Co-reporter:PaulE. Floreancig Dr.

Angewandte Chemie 2009 Volume 121( Issue 42) pp:7872-7875

Publication Date(Web):

DOI:10.1002/ange.200903480

Diastereoselective Tetrahydropyrone Synthesis through Transition-Metal-Free Oxidative CarbonHydrogen Bond Activation

Co-reporter:Wangyang Tu;Lei Liu ;PaulE. Floreancig

Angewandte Chemie 2008 Volume 120( Issue 22) pp:4252-4255

Publication Date(Web):

DOI:10.1002/ange.200706002

Total Synthesis of TheopederinD

Co-reporter:MichaelE. Green;JasonC. Rech ;PaulE. Floreancig

Angewandte Chemie 2008 Volume 120( Issue 38) pp:7427-7430

Publication Date(Web):

DOI:10.1002/ange.200802548

Total Synthesis of TheopederinD

Co-reporter:MichaelE. Green;JasonC. Rech ;PaulE. Floreancig

Angewandte Chemie International Edition 2008 Volume 47( Issue 38) pp:7317-7320

Publication Date(Web):

DOI:10.1002/anie.200802548

Diastereoselective Tetrahydropyrone Synthesis through Transition-Metal-Free Oxidative CarbonHydrogen Bond Activation

Co-reporter:Wangyang Tu;Lei Liu ;PaulE. Floreancig

Angewandte Chemie International Edition 2008 Volume 47( Issue 22) pp:4184-4187

Publication Date(Web):

DOI:10.1002/anie.200706002

Oxidative Cleavage in the Construction of Complex Molecules: Synthesis of the Leucascandrolide A Macrolactone

Co-reporter:Hyung Hoon Jung;John R. Seiders II;Paul E. Floreancig Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 44) pp:

Publication Date(Web):26 SEP 2007

DOI:10.1002/anie.200702999

Oxidation leads to macrolactone: Oxidative carbon–carbon bond activation is a key step in the formal synthesis of leucascandrolide A, which is formed in one step from 1. Additional features are stereoselective BiBr₃-mediated allylation, acetal formation as a fragment-coupling reaction, and a rhenium-mediated allylic alcohol transposition leading to stable macrolactol formation.

Oxidative Cleavage in the Construction of Complex Molecules: Synthesis of the Leucascandrolide A Macrolactone

Co-reporter:Hyung Hoon Jung;John R. Seiders II;Paul E. Floreancig Dr.

Angewandte Chemie 2007 Volume 119(Issue 44) pp:

Publication Date(Web):26 SEP 2007

DOI:10.1002/ange.200702999

Per Oxidation zum Makrolacton: Die oxidative Aktivierung einer Kohlenstoff-Kohlenstoff-Bindung ist der Schlüsselschritt in einer Formalsynthese von Leucascandrolid A, das in einer Stufe aus 1 entsteht. Erwähnenswert sind überdies eine stereoselektive BiBr₃-vermittelte Allylierung, eine Acetalbildung zur Fragmentkupplung sowie die Rhenium-vermittelte Verschiebung eines Allylalkohols vor der Bildung eines stabilen Makrolactols.

Total Synthesis of (+)-Dactylolide through an Efficient Sequential Peterson Olefination and Prins Cyclization Reaction

Co-reporter:Danielle L. Aubele;Shuangyi Wan Dr.

Angewandte Chemie 2005 Volume 117(Issue 22) pp:

Publication Date(Web):21 APR 2005

DOI:10.1002/ange.200500564

Schlüsselschritte in der Totalsynthese des Makrolid-Naturstoffs (+)-Dactylolid (siehe Struktur) sind zwei enantioselektive vinyloge Mukaiyama-Reaktionen, die Kupplung von Untereinheiten durch Acetalbildung, eine Sequenz aus Peterson-Olefinierung und Prins-Cyclisierung unter sehr milden Bedingungen sowie eine Mislow-Evans-Umlagerung zur Verschiebung einer Allylalkohol-Funktion.

Oxidatively generated electrophiles as initiators of epoxide cascade cyclization processes

Co-reporter:V. Satish Kumar, Shuangyi Wan, Danielle L. Aubele, Paul E. Floreancig

Tetrahedron: Asymmetry 2005 Volume 16(Issue 21) pp:3570-3578

Publication Date(Web):31 October 2005

DOI:10.1016/j.tetasy.2005.08.055

Total Synthesis of (+)-Dactylolide through an Efficient Sequential Peterson Olefination and Prins Cyclization Reaction

Co-reporter:Danielle L. Aubele;Shuangyi Wan Dr.

Angewandte Chemie International Edition 2005 Volume 44(Issue 22) pp:

Publication Date(Web):21 APR 2005

DOI:10.1002/anie.200500564

Key steps in the total synthesis of the macrolide natural product (+)-dactylolide (see formula) include two enantioselective vinylogous Mukaiyama reactions, fragment coupling through acetal formation, a sequential Peterson olefination/Prins cyclization reaction that proceeds under very mild conditions, and a Mislow–Evans rearrangement to effect the transposition of an allylic alcohol.

Catalytic Aerobic Generation of Acyliminium Ions through Electron-Transfer-Mediated Carbon-Carbon Bond Activation

Co-reporter:Danielle L. Aubele;Jason C. Rech;Paul E. Floreancig

Advanced Synthesis & Catalysis 2004 Volume 346(Issue 2-3) pp:

Publication Date(Web):29 MAR 2004

DOI:10.1002/adsc.200303173

Homobenzylic amides and carbamates, upon single-electron oxidation, undergo mesolytic cleavage reactions to form acyliminium ions. Appending nucleophilic groups to these substrates results in cyclization reactions to form N-acylaminals. The N-methylquinolinium ion that serves as the photooxidant in these reactions can function as a catalyst when dioxygen is introduced into these reactions, representing a unique method for effecting catalytic, aerobic oxidations. Herein we present a full account of our studies on catalytic aerobic electron-transfer-initiated cyclization reactions of homobenzylic amides and carbamates, with particular emphasis on the roles of the amide group, the nucleophilic group, and the functionality in the tether in promoting efficient ring constructions and altering reaction mechanisms.

Stereoselective piperidine synthesis through oxidative carbon–hydrogen bond functionalizations of enamides

Co-reporter:Gediminas J. Brizgys, Hyung Hoon Jung and Paul E. Floreancig

Chemical Science (2010-Present) 2012 - vol. 3(Issue 2) pp:NaN442-442

Publication Date(Web):2011/10/05

DOI:10.1039/C1SC00670C

Stereoselective heterocycle synthesis through a reversible allylic alcohol transposition and nucleophilic addition sequence

Co-reporter:Youwei Xie and Paul E. Floreancig

Chemical Science (2010-Present) 2011 - vol. 2(Issue 12) pp:NaN2427-2427

Publication Date(Web):2011/09/14

DOI:10.1039/C1SC00570G

Versatile approach to α-alkoxy carbamate synthesis and stimulus-responsive alcohol release

Co-reporter:R. Adam Mosey and Paul E. Floreancig