Electrophilic Chemistry of Biologically Important α-Ketoacids

Klumpp, Douglas A.; Lau, Siufu; Garza, Manuel; Schick, Brian; Kantardjieff, Katherine A.

doi:10.1021/jo9901945

Cited by 17 publications

(15 citation statements)

References 15 publications

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“…The identity of 12 was verified by comparison with an authentic sample of 12 (prepared from a different approach 8 ) and it was clear that condensation occurs exclusively at the 2-carbonyl group. The regiochemistry of condensation was also confirmed by X-ray crystallographic analysis.…”

Section: Resultsmentioning

confidence: 93%

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

Tracy

Abbott

Klumpp

2013

Synthetic Communications

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Section: Resultsmentioning

confidence: 93%

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

Tracy

Abbott

Klumpp

2013

Synthetic Communications

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“…When pyruvic acid is reacted with benzene in TFSA (Scheme 3), 1,1-diphenylethylene is formed as the major product. 4 The reaction proceeds with decarbonylation of intermediate acyl cation.…”

Section: Resultsmentioning

confidence: 99%

“…3 Recently, Klumpp described TFSA-catalyzed reactions of α-ketoacids with aromatic compounds. 4 It therefore seemed plausible that 1,2-dicarbonyl compounds would also react with reactive aromatic compounds other than benzene to form polymeric structures.…”

Section: Introductionmentioning

confidence: 99%

High-T_g Functional Aromatic Polymers

et al. 2015

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A novel series of linear, high-molecular-weight polymers and copolymers were synthesized by one-pot, metal-free superacid-catalyzed polymerization of aliphatic 1,2-diketones (2,3-butanedione (1a), 2,3-hexadione (1b), 3,4-hexadione (1c), 2,3-butanedione monoxime (1d), pyruvic acid (1e), 1,4-dibromo-2,3-butanedione (1f), 2-bromopyruvic acid (1g), and methyl-3,3,3-trifluoropyruvate (1h) with linear, nonactivated, multiring aromatic hydrocarbons terphenyl (A), biphenyl (B), fluorene (C), and N-ethyl carbazole (D). Depending on the reaction system, the polymerizations were carried out as stoichiometric or non stoichiometric, with direct or inverse monomer addition. Copolymers were obtained by polymerization of 1,2-diketones with a mixture of aromatic hydrocarbons. In the course of the polymerization only one carbonyl group of a 1,2-diketone reacts to form C−C bonds with aromatic fragments while the other functional groups (including the second carbonyl group) are incorporated unchanged into polymer chain. The polymerizations performed at room temperature in the Brønsted superacid CF 3 SO 3 H (TFSA) and in a mixture of TFSA with methylene chloride or trifluoroacetic acid (TFA) tolerant of carbonyl, acetyl, N-oxime, carboxy, methoxy, and bromomethyl groups. The polymers obtained were soluble in most common organic solvents, and flexible transparent, colorless films could be cast from the solutions. 1 H and 13 C NMR analyses of the polymers synthesized revealed high regio-selectivity of the polymerizations and yielded linear structures with para-substitution in the phenylene fragments of the main chains. An electron affinity (EA) of the carbonyl component and the heterolytic C−O bond dissociation energy (DE) in carbinol 3 (correlating with the activation energy of carbocation 4 formation) have been used to rationalize the reactivity of carbonyl components. The calculations show the following reactivity order of the diketones. 1f > 1g ≈ 1e> 1a> 1d > 1h> 1b>1c which is totally in agreement with the experimental data. The new functional polymers obtained demonstrate good processability, high T g and thermal stability. Unexpected white light emission was observed for polymer 2gA.

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“…This high and renewed interest is also attributed to the fact that the involvement of superelectrophilic species [2] in triflic acid-mediated transformations has been often implicated and, in fact, superelectrophiles have been detected by 1 H and 13 C NMR spectroscopy [3][4][5]. Triflic acid has been proved to be particularly useful in various alkylation processes [6][7][8][9][10] and in varied cyclization reactions including the synthesis of carbocyclic [9,[11][12][13][14] and heterocyclic multiple ring systems [3,10,15,16]. These results have considerably widened the scope of the use of triflic acid in synthetic processes and resulted in a better understanding of the mechanistic background of the catalyzed transformations.…”

Section: Introductionmentioning

confidence: 99%

Fused Polycyclic Hydrocarbons Through Superacid-Induced Cyclialkylation of Aromatics

2007

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Benzene and substituted derivatives (toluene, ortho-xylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, anisole), when applied in large excess, react with 1,4 diols (pentan-1,4-diol, hexan-2,5-diol, and 2,5-dimethylhexan-2,5-diol) or an oxolane (2,2,5,5-tetramethyltetra hydrofuran) in the presence of the Brønsted superacid trifluoromethanesulfonic acid (triflic acid, TFSA) to afford substituted tetralins in excellent yields with high selectivity. Reacting benzene with a small excess of alkylating agents yields octahydroanthracenes. The transformation of naphthalene with oxolane leads to a partially saturated octamethyloctahydrotetracene under similar conditions. Product formation is interpreted by intermolecular FriedelCrafts alkylation followed by cyclialkylative ring closure.

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Electrophilic Chemistry of Biologically Important α-Ketoacids

Cited by 17 publications

References 15 publications

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

High-T_g Functional Aromatic Polymers

Fused Polycyclic Hydrocarbons Through Superacid-Induced Cyclialkylation of Aromatics

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Electrophilic Chemistry of Biologically Important α-Ketoacids

Cited by 17 publications

References 15 publications

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

Superacid-Promoted Hydroxyalkylation of 1,2-Indandiones

High-Tg Functional Aromatic Polymers

Fused Polycyclic Hydrocarbons Through Superacid-Induced Cyclialkylation of Aromatics

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Product

Resources

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High-T_g Functional Aromatic Polymers