Silver-Catalyzed Formal Inverse Electron-Demand Diels–Alder Reaction of 1,2-Diazines and Siloxy Alkynes

Türkmen, Yunus E.; Montavon, Timothy J.; Kozmin, Sergey A.; Rawal, Viresh H.

doi:10.1021/ja302537j

Cited by 78 publications

(57 citation statements)

References 57 publications

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“…According to the literatures, the Diels-Alder cyclization reactions relied on Lewis acidity of the catalysts to a great extent [52][53][54][55][56][57]. Lewis acid site were able to activate enone dienophiles by lowering the activation barrier in the Diels-Alder reactions of enones [55].…”

Section: Catalytic Conversion Of Soybean Oilmentioning

confidence: 99%

Quantitative conversion of triglycerides to hydrocarbons over hierarchical ZSM-5 catalyst

Chen

Wang

Zhang

et al. 2015

Applied Catalysis B: Environmental

113

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Section: Catalytic Conversion Of Soybean Oilmentioning

confidence: 99%

Quantitative conversion of triglycerides to hydrocarbons over hierarchical ZSM-5 catalyst

Chen

Wang

Zhang

et al. 2015

Applied Catalysis B: Environmental

113

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“…illustrates the chemical route of the DAR inv of 1,2-diazine 23 and siloxy alkyn 24 to the silyl-protected 2-naphthol (modified from Turkmen 53 ).…”

Section: Methodsmentioning

confidence: 99%

“…An example for a silver-catalyzed reaction phthalazines 23 and siloxy alkynes 24, reacting under loss of nitrogen to silylprotected 2-naphthols 26 53 is shown in Scheme 5.…”

Section: Synthesis Of Triazine Componentsmentioning

confidence: 99%

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2013

IJPSR

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ABSTRACT:Here, we review the development of prospective image processing systems in molecular diagnostics and of pharmacologically active ingredients for patient-specific therapeutic approaches. These projects require not only high demands on quality, safety, and specificity but also, rapid, efficient and irreversible ligation routes during the synthesis of future pharmaceuticals. The Diels-Alder ligation reaction with inverse electron demand (DAR inv ) is an eligible technology not restricted to medical applications, but valuable in selective modification by functionalization of polymers, organic and inorganic surfaces and micro arrays. Additionally, the DAR inv technology is considered as an attractive strategy-platform for efficient syntheses of promising pharmacologically active components and derivatives of natural molecules with an optimized therapeutic index. We like to encourage scientists working with the brilliant concept of Sharpless"s "Click chemistry", to intensify their research with this valuable DAR inv technology able to open the door for regioselective, stereospecific, and bioorthogonal exigent syntheses of substances of highest quality inconceivable so far.

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“…[2] Herein, we describe the discovery and development of a formal [2+2+2] cycloaddition of siloxy alkynes with phthalazines, a process that had not been previously described for either 1,2-diazines or electron-rich alkynes. [3][4][5][6][7] This effort has not only afforded heterocyclic products with a unique pentacyclic ring system but has also enabled the identification of a novel chemotype that inhibits glycolytic ATP production by direct blockage of glucose uptake in CHO-K1 cells. As a result of the prevalence of the Warburg effect in many human cancers, such compounds may prove useful in the development of new therapeutics which target reprogrammed energy metabolism of rapidly proliferating cells.…”

mentioning

confidence: 99%

[2+2+2] Cycloadditions of Siloxy Alkynes with 1,2‐Diazines: From Reaction Discovery to Identification of an Antiglycolytic Chemotype

Montavon¹,

Türkmen²,

Shamsi³

et al. 2013

Angewandte Chemie

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The synthesis of new nitrogen-containing heterocycles plays a pivotal role in chemical biology and medicinal chemistry, as reflected by their many applications in the development of pharmacological probes and drugs. [1] Despite notable progress, there is a significant need for the identification of new nitrogen heterocycles which target previously unexplored regions of biogenic chemical space. Among the many possible synthetic strategies to such compounds, cycloadditions involving C-N multiple bonds are particularly attractive as they generate complex cyclic products by simultaneous formation of multiple bonds starting from readily available precursors. [2] Herein, we describe the discovery and development of a formal [2+2+2] cycloaddition of siloxy alkynes with phthalazines, a process that had not been previously described for either 1,2-diazines or electron-rich alkynes. [3][4][5][6][7] This effort has not only afforded heterocyclic products with a unique pentacyclic ring system but has also enabled the identification of a novel chemotype that inhibits glycolytic ATP production by direct blockage of glucose uptake in CHO-K1 cells. As a result of the prevalence of the Warburg effect in many human cancers, such compounds may prove useful in the development of new therapeutics which target reprogrammed energy metabolism of rapidly proliferating cells. [8] Our study began by examining the reaction of phthalazine (1) with the siloxy alkyne 2 in the presence of common Brønsted acids. While no reaction between 1 and 2 was observed in the absence of such additives, even at elevated temperatures, we found that addition of simple pyridinium salts promoted the formation of a new pentacyclic product (3; Scheme 1).After examining a range of mono-and bis(pyridinium) salts in various solvents, we determined the optimum protocol to entail the use of a stoichiometric amount of pyridinium trifluoromethanesulfonimide in CH 2 Cl 2 at room temperature, thus producing the lactam 3 as a single diastereomer in 77 % yield. While most of the known [2+2+2] cycloadditions typically require the presence of a transition-metal catalyst, [9] the present method promotes the condensation under remarkably mild reaction conditions, using only a simple, weak Brønsted acid. The excellent diastereoselectivity of this transformation is also highly noteworthy. The atom connectivity within the reaction product was initially determined to be that in 3 and is based on extensive use of NMR spectroscopic methods. Ultimately, the structure was secured and the relative stereochemistry of the three newly created stereogenic centers was defined through X-ray crystallographic analysis (see below).Interestingly, while a range of substituted mono-and bis(pyridinium) trifluoromethanesulfonimides were found to be effective as reaction promoters, the use of only HNTf 2 , in the absence of pyridine, produced 3 with lower efficiency (48 % yield) and diminished diastereoselectivity (83:17). Furthermore, the use of either pyridinium chloride, pyridinium p-toluenesulfo...

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Silver-Catalyzed Formal Inverse Electron-Demand Diels–Alder Reaction of 1,2-Diazines and Siloxy Alkynes

Cited by 78 publications

References 57 publications

Quantitative conversion of triglycerides to hydrocarbons over hierarchical ZSM-5 catalyst

Quantitative conversion of triglycerides to hydrocarbons over hierarchical ZSM-5 catalyst

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[2+2+2] Cycloadditions of Siloxy Alkynes with 1,2‐Diazines: From Reaction Discovery to Identification of an Antiglycolytic Chemotype

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