D. Tyler McQuade

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Organization: Florida State University

Department: Department of Chemistry & Biochemistry

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Chemicals
References

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

Co-reporter:Dr. Alina Dragulescu-Andrasi;Dr. L. Zane Miller;Dr. Banghao Chen; D. Tyler McQuade; Michael Shatruk

Angewandte Chemie International Edition 2016 Volume 55( Issue 12) pp:3904-3908

Publication Date(Web):

DOI:10.1002/anie.201511186

Abstract

Soluble polyphosphide anions were successfully generated in a number of organic solvents by the reaction between shelf-stable red phosphorus and potassium ethoxide. The species were identified by ³¹P NMR spectroscopy in solution and by X-ray crystal-structure determination of (Bu₄N)₂P₁₆ in the solid state. The reaction was scaled up to gram quantities by using a flow-chemistry process.

Frontispiece: Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

Co-reporter:Dr. Alina Dragulescu-Andrasi;Dr. L. Zane Miller;Dr. Banghao Chen; D. Tyler McQuade; Michael Shatruk

Angewandte Chemie International Edition 2016 Volume 55( Issue 12) pp:

Publication Date(Web):

DOI:10.1002/anie.201681261

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

Co-reporter:Dr. Alina Dragulescu-Andrasi;Dr. L. Zane Miller;Dr. Banghao Chen; D. Tyler McQuade; Michael Shatruk

Angewandte Chemie 2016 Volume 128( Issue 12) pp:3972-3976

Publication Date(Web):

DOI:10.1002/ange.201511186

Abstract

Frontispiz: Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide

Co-reporter:Dr. Alina Dragulescu-Andrasi;Dr. L. Zane Miller;Dr. Banghao Chen; D. Tyler McQuade; Michael Shatruk

Angewandte Chemie 2016 Volume 128( Issue 12) pp:

Publication Date(Web):

DOI:10.1002/ange.201681261

Synthesis and Reactivity Profile of Ylidenemalononitrile Enamines and Their Ester Analogs Towards Electrophiles and Nucleophiles

Co-reporter:Ashley R. Longstreet, Daniel Rivalti, and D. Tyler McQuade

The Journal of Organic Chemistry 2015 Volume 80(Issue 17) pp:8583-8596

Publication Date(Web):July 28, 2015

DOI:10.1021/acs.joc.5b01169

Herein, we describe the synthesis and reactivity of enamines derived from ylidenemalononitriles and ylidenecyanoacetates. The enamine scope was expanded by (1) increasing yields of aldehyde-derived ylidenemalononitriles, (2) incorporating silyl functionalities, and (3) using other amide acetals to expand the substitution patterns of pyridines resulting from enamine cyclization. In addition, methods to produce α-pyrones and polysubstituted pyridines from both ylidenemalononitriles and ylidenecyanoacetates are described.

Ylidenemalononitrile Enamines as Fluorescent “Turn-On” Indicators for Primary Amines

Co-reporter:Ashley R. Longstreet ; Minyoung Jo ; Rebecca R. Chandler ; Kenneth Hanson ; Naiqian Zhan ; Jeremy J. Hrudka ; Hedi Mattoussi ; Michael Shatruk

Journal of the American Chemical Society 2014 Volume 136(Issue 44) pp:15493-15496

Publication Date(Web):October 14, 2014

DOI:10.1021/ja509058u

Ylidenemalononitrile enamines undergo rapid amine exchange followed by a cyclization with primary amines to yield fluorescent products with emission intensities as high as 900 times greater than the starting materials. After identifying the fluorescent species by X-ray crystallography, we demonstrate that the rate of amine exchange is substrate dependent and that by simple structural variation the fluorescence can be tuned over the entire visible spectrum. We further demonstrate their potential application in biomolecule labeling.

Alkali metal oxides trapped by diethylzinc

Co-reporter:L. Zane Miller, Michael Shatruk and D. Tyler McQuade

Chemical Communications 2014 vol. 50(Issue 64) pp:8937-8940

Publication Date(Web):13 Jun 2014

DOI:10.1039/C4CC02929A

Reactions of alkali metal hydroxides with neat diethyl zinc lead to the formation of oxo-centered clusters M2O(ZnEt2)n (M = Na, n = 3 or M = K, Rb, n = 4). These molecules crystallize in highly symmetric space groups, forming extended structures supported by weak M–H interactions. We discuss the mechanistic implications and relationship of these structures to known (oxo)organozincates.

Continuous Synthesis of Organozinc Halides Coupled to Negishi Reactions

Co-reporter:Nerea Alonso;L. Zane Miller;Juan deM.Muñoz;Jesus Alcázar

Advanced Synthesis & Catalysis 2014 Volume 356( Issue 18) pp:3737-3741

Publication Date(Web):

DOI:10.1002/adsc.201400243

Cover Picture: Continuous Synthesis of Organozinc Halides Coupled to Negishi Reactions (Adv. Synth. Catal. 18/2014)

Co-reporter:Nerea Alonso;L. Zane Miller;Juan deM.Muñoz;Jesus Alcázar

Advanced Synthesis & Catalysis 2014 Volume 356( Issue 18) pp:

Publication Date(Web):

DOI:10.1002/adsc.201401043

Organic Reaction Systems: Using Microcapsules and Microreactors to Perform Chemical Synthesis

Co-reporter:Ashley R. Longstreet and D. Tyler McQuade

Accounts of Chemical Research 2013 Volume 46(Issue 2) pp:327

Publication Date(Web):October 16, 2012

DOI:10.1021/ar300144x

The appetite for complex organic molecules continues to increase worldwide, especially in rapidly developing countries such as China, India, and Brazil. At the same time, the cost of raw materials and solvent waste disposal is also growing, making sustainability an increasingly important factor in the production of synthetic life-saving/improving compounds. With these forces in mind, our group is driven by the principle that how we synthesize a molecule is as important as which molecule we choose to synthesize. We aim to define alternative strategies that will enable more efficient synthesis of complex molecules. Drawing our inspiration from nature, we attempt to mimic (1) the multicatalytic metabolic systems within cells using collections of nonenzyme catalysts in batch reactors and (2) the serial synthetic machinery of fatty acid/polyketide biosynthesis using microreactor systems. Whether we combine catalysts in batch to prepare an active pharmaceutical ingredient (API) or use microreactors to synthesize small or polymeric molecules, we strive to understand the mechanism of each reaction while also developing new methods and techniques.This Account begins by examining our early efforts in the development of novel catalytic materials and characterization of catalytic systems and how these observations helped forge our current models for developing efficient synthetic routes. The Account progresses through a focused examination of design principles needed to develop multicatalyst systems using systems recently published by our group as examples. Our systems have been successfully applied to produce APIs as well as new synthetic methods. The multicatalyst section is then juxtaposed with our work in continuous flow multistep synthesis. Here, we discuss the design principles needed to create multistep continuous processes using examples from our recent efforts. Overall, this Account illustrates how multistep organic routes can be conceived and achieved using strategies and techniques that mimic biological systems.

Improved Synthesis of Mono- and Disubstituted 2-Halonicotinonitriles from Alkylidene Malononitriles

Co-reporter:Ashley R. Longstreet, Brian S. Campbell, B. Frank Gupton, and D. Tyler McQuade

Organic Letters 2013 Volume 15(Issue 20) pp:5298-5301

Publication Date(Web):October 4, 2013

DOI:10.1021/ol4025265

Pyridines with 2,3,4 and/or 5 substitution remain challenging to prepare. Existing strategies to form multisubstituted 2-halonicotinonitriles via enamines suffer from dimerization of the starting alkylidene malononitriles resulting in low yields. Through alteration of reaction conditions, a new high yielding method into enamines was realized by condensing DMF–DMA and alkylidene malononitriles in the presence of substoichiometric acetic anhydride. Cyclization of the resulting enamines under Pinner conditions provided 2-halonicotinonitriles in high overall yields.

Continuous Synthesis and Use of N-Heterocyclic Carbene Copper(I) Complexes from Insoluble Cu2O

Co-reporter:Suzanne M. Opalka, Jin Kyoon Park, Ashley R. Longstreet, and D. Tyler McQuade

Organic Letters 2013 Volume 15(Issue 5) pp:996-999

Publication Date(Web):February 13, 2013

DOI:10.1021/ol303442m

It is demonstrated that homogeneous N-heterocyclic carbene–copper(I)-chloride complexes can be prepared continuously by flowing NHC precursors through a packed bed of solid Cu2O suspended in molecular sieves. The method enables the synthesis of a wide range of complexes including those that are challenging to prepare using standard approaches. Our strategy enables both sustained output of complex production for long-term catalytic reactions (greater than 5 h) and for generation of gram quantities for storage (greater than 1 g of complex in ∼16 min).

Copper(I)/N-Heterocyclic Carbene (NHC)-Catalyzed Addition of Terminal Alkynes to Trifluoromethyl Ketones for Use in Continuous Reactors

Co-reporter:Camille A. Correia;Peter H. Seeberger

Advanced Synthesis & Catalysis 2013 Volume 355( Issue 18) pp:3517-3521

Publication Date(Web):

DOI:10.1002/adsc.201300802

Fluorescent THF-Based Fructose Analogue Exhibits Fructose-Dependent Uptake

Co-reporter:Dr. Marina Tanasova;Matthew Plutschack;Megan E. Muroski; Shana J. Sturla; Geoffrey F. Strouse; D. Tyler McQuade

ChemBioChem 2013 Volume 14( Issue 10) pp:1263-1270

Publication Date(Web):

DOI:10.1002/cbic.201300164

Abstract

Recent publications suggest that high dietary fructose might play a significant role in cancer metabolism and can exacerbate a number of aspects of metabolic syndrome. Addressing the role that fructose plays in human health is a controversial question and requires a detailed understanding of many factors including the mechanism of fructose transport into healthy and diseased cells. Fructose transport into cells is thought to be largely mediated by the passive hexose transporters Glut2 and Glut5. To date, no probes that can be selectively transported by one of these enzymes but not by the other have been identified. The data presented here indicate that, in MCF-7 cells, a 1-amino-2,5-anhydro-D-mannitol-based fluorescent NBDM probe is transported twice as efficiently as fructose and that this takes place with the aid of Glut5. Its Glut5 specificity and differential uptake in cancer cells and in normal cells suggest this NBDM probe as a potentially useful tool for cross-cell-line correlation of Glut5 transport activity.

Synthesis of Optically Active 4-Substituted 2-Cyclohexenones

Co-reporter:Tania I. Houjeiry, Sarah L. Poe, and D. Tyler McQuade

Organic Letters 2012 Volume 14(Issue 17) pp:4394-4397

Publication Date(Web):August 17, 2012

DOI:10.1021/ol301874x

Recently, Nicolaou and Baran independently synthesized optically active 4-substituted 2-cyclohexenones via an efficient LiOH-mediated intramolecular aldol condensation. Thus far, application of their cyclization approach has been limited to ketoaldehydes where the R-group is branched. It is demonstrated that the LiOH-mediated cyclization, when applied to substrates containing unbranched R-groups, results in significant erosion of optical purity. A mechanistic justification is provided, and a set of neutral, organocatalyzed conditions is identified that enables cyclization with little loss in optical purity.

Regioselective Catalytic Hydroboration of Propargylic Species Using Cu(I)-NHC Complexes

Co-reporter:Jin Kyoon Park, Brian A. Ondrusek, and D. Tyler McQuade

Organic Letters 2012 Volume 14(Issue 18) pp:4790-4793

Publication Date(Web):September 4, 2012

DOI:10.1021/ol302086v

The catalytic regioselective hydroboration of propargylic alcohols and ethers was investigated using NHC-CuCl. We observe that different NHC-CuCl complexes catalyze hydroborations of propargylic substrates with opposite regioselectivity. A 6-NHC-CuCl complex provides α-selectivity whereas β-selectivity is achieved using a 5-NHC-CuCl complex. The reaction tolerates a wide range of functional groups.

Iterative Asymmetric Allylic Substitutions: syn- and anti-1,2-Diols through Catalyst Control

Co-reporter:Dr. Jin Kyoon Park ;Dr. D. Tyler McQuade

Angewandte Chemie 2012 Volume 124( Issue 11) pp:2771-2775

Publication Date(Web):

DOI:10.1002/ange.201107874

Iterative Asymmetric Allylic Substitutions: syn- and anti-1,2-Diols through Catalyst Control

Co-reporter:Dr. Jin Kyoon Park ;Dr. D. Tyler McQuade

Angewandte Chemie International Edition 2012 Volume 51( Issue 11) pp:2717-2721

Publication Date(Web):

DOI:10.1002/anie.201107874

Stereoconvergent Synthesis of Chiral Allylboronates from an E/Z Mixture of Allylic Aryl Ethers Using a 6-NHC−Cu(I) Catalyst

Co-reporter:Jin Kyoon Park ; Hershel H. Lackey ; Brian A. Ondrusek

Journal of the American Chemical Society 2011 Volume 133(Issue 8) pp:2410-2413

Publication Date(Web):February 3, 2011

DOI:10.1021/ja1112518

We present a 6-NHC−Cu(I) complex that provides α-substituted allylboronates using allylic aryl ether substrates. The method was discovered by comparison of the chemoselectivities exhibited by complexes 1a, 1b, 2, and 3. We observed that 1a preferentially reacts with electron-rich alkenes over electron-deficient alkenes. Development of an asymmetric method revealed that 1b reacts with both the E and Z isomers to provide the same absolute configuration without showing E−Z isomerization. This stereoconvergent reaction occurs with high yields (av 86%), high SN2′ selectivity (>99:1), and high ee (av 94%) and exhibits wide functional-group tolerance using pure E or Z isomer or E/Z alkene mixtures. The stereoconvergent feature enables the use of many different olefination strategies for substrate production, including cross-metathesis. Chiral allylboronates could be purified by silica gel chromatography and stored in the freezer without decomposition.

Thiourea/Proline Derivative-Catalyzed Synthesis of Tetrahydrofuran Derivatives: A Mechanistic View

Co-reporter:Suzanne M. Opalka, Jeremy L. Steinbacher, Brandon A. Lambiris, and D. Tyler McQuade

The Journal of Organic Chemistry 2011 Volume 76(Issue 16) pp:6503-6517

Publication Date(Web):June 9, 2011

DOI:10.1021/jo200838v

A thiourea/proline derivative-catalyzed synthesis of linear α-substituted tetrahydrofuran/pyran derivatives starting with lactol substrates is presented. This study demonstrates the utility and potential complications of using (thio)urea/proline cocatalysis as each of these catalysts is necessary to provide the observed reactivity, but a time-dependent decrease in enantioselectivity is observed. New mechanistic insights into (thio)urea/proline cocatalysis are presented.

A Chiral 6-Membered N-Heterocyclic Carbene Copper(I) Complex That Induces High Stereoselectivity

Co-reporter:Jin Kyoon Park, Hershel H. Lackey, Matthew D. Rexford, Kirill Kovnir, Michael Shatruk, and D. Tyler McQuade

Organic Letters 2010 Volume 12(Issue 21) pp:5008-5011

Publication Date(Web):October 4, 2010

DOI:10.1021/ol1021756

A chiral 6-membered annulated N-heterocyclic (6-NHC) copper complex that catalyzes β-borylations with high yield and enantioselectivity was developed. The chiral 6-NHC copper complex is easy to prepare on the gram scale and is very active, showing 10 000 turnovers at 0.01 mol % of catalyst without significant decrease of enantioselectivity and with useful reaction rates.

The Continuous-Flow Synthesis of Ibuprofen

Co-reporter:AndrewR. Bogdan;SarahL. Poe;DanielC. Kubis;StevenJ. Broadwater;D.Tyler McQuade

Angewandte Chemie International Edition 2009 Volume 48( Issue 45) pp:8547-8550

Publication Date(Web):

DOI:10.1002/anie.200903055

The Continuous-Flow Synthesis of Ibuprofen

Co-reporter:AndrewR. Bogdan;SarahL. Poe;DanielC. Kubis;StevenJ. Broadwater;D.Tyler McQuade

Angewandte Chemie 2009 Volume 121( Issue 45) pp:8699-8702

Publication Date(Web):

DOI:10.1002/ange.200903055

Creating microenvironments using encapsulated polymers

Co-reporter:Muris Koba&x161;lija;Andrew R. Bogdan;Sarah L. Poe;Ferno Escobedo

Journal of Polymer Science Part A: Polymer Chemistry 2008 Volume 46( Issue 7) pp:2309-2315

Publication Date(Web):

DOI:10.1002/pola.22630

Abstract

Miscible solvents are phase separated within microcapsules containing entrapped polymers, thereby creating stable, isolated microenvironments. In particular, we demonstrate that encapsulated polyethyleneimine induces phase separation of toluene and methanol and that this phase separation is well modeled by the Flory-Huggins theory. We further show the generality of microenvironment formation by phase separating tetrahydrofuran and acetone with entrapped polystyrene. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2309–2315, 2008

Alkali metal oxides trapped by diethylzinc

Co-reporter:L. Zane Miller, Michael Shatruk and D. Tyler McQuade

Chemical Communications 2014 - vol. 50(Issue 64) pp:NaN8940-8940

Publication Date(Web):2014/06/13

DOI:10.1039/C4CC02929A