Cyclic Guanidine Organic Catalysts: What Is Magic About Triazabicyclodecene?

Kiesewetter, Matthew K.; Scholten, Marc D.; Kirn, Nicole; Weber, Ryan L.; Hedrick, James L.; Waymouth, Robert M.

doi:10.1021/jo902369g

Cited by 187 publications

(162 citation statements)

References 79 publications

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“…To favor high conversion we therefore conducted the polymerizations in bulk monomer at room temperature using the highly active organocatalyst triazabicyclodecene (TBD) (Fig. 3) (39) resulted in the rapid production of poly(βMδVL)-within 1 h at room temperature (T = 18°C) 75% of the monomer was consumed, within 3 h the reaction approached equilibrium (Fig. S2).…”

Section: Construction Of a Nonnatural Metabolic Pathway For Biosynthementioning

confidence: 99%

Scalable production of mechanically tunable block polymers from sugar

Xiong¹,

Schneiderman

Bates³

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

162

205

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Significance In recent years there has been extensive research toward the development of sustainable polymeric materials. However, environmentally benign, bioderived polymers still represent a woefully small fraction of plastics and elastomers on the market today. To displace the widely useful oil-based polymers that currently dominate the industry, a bioderived synthetic polymer must be both cost and performance competitive. In this paper we address this challenge by combining the efficient bioproduction of β-methyl-δ-valerolactone with controlled polymerization techniques to produce economically viable block polymer materials with mechanical properties akin to commercially available thermoplastics and elastomers.

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Section: Construction Of a Nonnatural Metabolic Pathway For Biosynthementioning

confidence: 99%

Scalable production of mechanically tunable block polymers from sugar

Xiong¹,

Schneiderman

Bates³

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

162

205

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“…In order to potentially improve the properties of our compounds, we converted the ester group of the derivatives 2 into the corresponding better water soluble amides 10 with a one-step TBD-catalyzed amidation procedure (Scheme 5). 26 In our previous studies, amidation of the indole-2-carboxylate gave often improved water solubility. 24 …”

mentioning

confidence: 94%

2,3′-Bis(1′H-indole) heterocycles: New p53/MDM2/MDMX antagonists

Neochoritis

Wang

Estrada‐Ortiz

et al. 2015

Bioorganic & Medicinal Chemistry Letters

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The protein-protein interaction of p53 and MDM2/X is a promising non genotoxic anticancer target. A rapid and efficient methodology was developed to synthesize the 2,3'-bis(1'H-indole) heterocyclic scaffold 2 as ester, acid and amide derivatives. Their binding affinity with MDM2 was evaluated using both fluorescence polarization (FP) assay and HSQC experiments, indicating good inhibition and a perfect starting point for further optimizations.

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“…As a well-known guanidine in ringopening polymerization of esters, [20] the catalysis of 1,5,7-triazabicyclo [4.4.0]dec-5-ene (TBD) is supposed to have two alternative mechanisms namely nucleophilic catalysis through covalently bound and acid-base catalysis via H bonding. [21][22][23][24] Besides, TBD could catalyze the intramolecular aldol reaction of ketoaldehydes as a general base. [25] At present, the novel bicyclic chiral guanidine bearing a hydroxyl group designed by Misaki et al [17] has been applied in asymmetric 1,4-addition of 5H-oxazol-4-ones to alkynyl carbonyl compounds (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Theoretical study of enantiomeric and geometric control in chiral guanidine-catalyzed asymmetric 1,4-addition of 5H -oxazol-4-ones

Wang

2013

Int. J. Quantum Chem

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Density functional theory calculations are used to study the reaction mechanism and origins of high stereoselectivity in chiral guanidine-catalyzed asymmetric 1,4-addition of 5H-oxazol-4-ones. The reaction involves proton abstraction of 5H-oxazol-4-one, CAC bond formation, and proton transfer. N1 atom of chiral guanidine exchanges its character as base and acid to activate 5H-oxazol-4-one and to facilitate the product formation. The role of N2AH2 is not only H-bond donor for 5H-oxazol-4-one but also electron accepter for N1. The enantioselectivity related with rate-limiting step 1 and Z/E selectivity determined in step 2 are primarily influenced by a five to six-membered ring link in the backbone of chiral guanidine. The reaction proceeds along the favorable path with smaller rotations of the linked bonds. The enantioselectivity is improved with guanidine involving an electron-deficient and bulky substituent. With methyl etherprotected hydroxy in structure, the catalytic ability and enantioselective control of guanidine are extraordinarily low, affording the opposite enantiomer as major product. Zisomers are preferred in all cases.

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Cyclic Guanidine Organic Catalysts: What Is Magic About Triazabicyclodecene?

Cited by 187 publications

References 79 publications

Scalable production of mechanically tunable block polymers from sugar

Scalable production of mechanically tunable block polymers from sugar

2,3′-Bis(1′H-indole) heterocycles: New p53/MDM2/MDMX antagonists

Theoretical study of enantiomeric and geometric control in chiral guanidine-catalyzed asymmetric 1,4-addition of 5H -oxazol-4-ones

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