Ashwin R Bharadwaj

Northwest University, Evanston, Illinois, United States

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Publications (6)42.74 Total impact

  • Troy E Reynolds, Ashwin R Bharadwaj, Karl A Scheidt
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    ABSTRACT: Silyloxyallenes derived from alpha-hydroxypropargylsilanes undergo efficient addition to aldehydes with catalytic amounts of Lewis acids. The allenes are accessed from the corresponding propargylsilanes in a base-catalyzed 1,2-Brook rearrangement/SE2' process. Enantioenriched propargylsilanes are synthesized by a new zinc-promoted addition of alkynes to acylsilanes in up to 74% ee. This work demonstrates that conversion to the silyloxyallenes occurs with minimal erosion in optical activity. The use of a chiral chromium(III) Lewis acid effects the catalytic asymmetric addition of racemic silyloxyallenes to aromatic aldehydes in up to 92% ee. The overall reaction is broad in scope and accommodates a wide variety of aromatic and aliphatic substituents on both the propargylsilane and aldehyde.
    Journal of the American Chemical Society 01/2007; 128(48):15382-3. · 10.68 Impact Factor
  • Troy E. Reynolds, Ashwin R. Bharadwaj, Karl A. Scheidt
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    ABSTRACT: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
    ChemInform 01/2007; 38(15).
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    ABSTRACT: A strategy utilizing N-heterocyclic carbenes (NHCs) derived from thiazolium salts has been developed for the generation of carbonyl anions from acylsilanes. Synthetically useful 1,4-diketones and N-phosphinoyl-alpha-aminoketones have been prepared in good to excellent yields via NHC-catalyzed additions of acylsilanes to the corresponding alpha,beta-unsaturated systems and N-phosphinoylimines. These organocatalytic reactions are air- and water-tolerant methods to execute robust carbonyl anion addition reactions. Additionally, polysubstituted aromatic furans and pyrroles have been efficiently synthesized in a one-pot process using this carbonyl anion methodology. The addition of alcohols to the reaction renders the process catalytic in thiazolium salt. In an effort to synthesize a potential intermediate along the proposed reaction pathway, silylated thiazolium carbinols have been identified to provide good yields of carbonyl anion addition products when subjected to the standard reaction conditions in the presence of suitable electrophiles.
    The Journal of Organic Chemistry 08/2006; 71(15):5715-24. · 4.56 Impact Factor
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    ABSTRACT: The conjugate addition of carbonyl anions catalyzed by thiazolium salts that is fully operative under neutral aqueous conditions has been accomplished. The combination of alpha-keto carboxylates and thiazolium-derived zwitterions produces reactive carbonyl anions in a buffered protic environment that readily undergo conjugate additions to substituted alpha,beta-unsaturated 2-acyl imidazoles. The scope of the reaction has been examined and found to accommodate various alpha-keto carboxylates and beta-aryl substituted unsaturated 2-acyl imidazoles. The optimal precatalyst for this process is the commercially available thiazolium salt 5, a simple analogue of thiamin diphosphate. In this process, no benzoin products from carbonyl anion dimerization are observed. The corresponding 1,4-dicarbonyl compounds can be efficiently converted into esters and amides by way of activation of the N-methylimidazole ring via alkylation.
    Journal of the American Chemical Society 11/2005; 127(42):14675-80. · 10.68 Impact Factor
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    Ashwin R Bharadwaj, Karl A Scheidt
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    ABSTRACT: [reaction: see text] A multicomponent synthesis of highly substituted pyrroles catalyzed by thiazolium salts has been disclosed. The reaction employs an acyl anion conjugate addition reaction of acylsilanes (sila-Stetter) and unsaturated ketones to generate 1,4-dicarbonyl compounds in situ. The subsequent addition of various amines promotes a Paal-Knorr reaction, affording the desired pyrrole nucleus in an efficient one-pot process.
    Organic Letters 08/2004; 6(14):2465-8. · 6.14 Impact Factor
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    Anita E Mattson, Ashwin R Bharadwaj, Karl A Scheidt
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    ABSTRACT: A new acyl anion addition reaction between acylsilanes and alpha,beta-unsaturated conjugate acceptors promoted by a nucleophilic organic catalyst has been disclosed. The 1,4-dicarbonyl products produced in this reaction are highly useful synthons. Neutral carbenes (or zwitterions) generated in situ from commercial thiazolium salts are used as effective catalysts for the reaction which is in contrast to established anionic catalysts typically employed to promote the required Brook rearrangement (1,2-silyl shift from carbon to oxygen) involved in the reported reaction. This process successfully utilizes acylsilanes as tunable acyl anion progenitors and is tolerant of a wide range of structural diversity on the acylsilane or the conjugate acceptor.
    Journal of the American Chemical Society 04/2004; 126(8):2314-5. · 10.68 Impact Factor