Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement
| Autor: | Javier Read de Alaniz, Diana Yu, Ryan Chung, Jason E. Hein, Alyssa F. Jones, Van T. Thai, Gesine K. Veits |
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| Rok vydání: | 2015 |
| Předmět: |
Reaction mechanism
aza-Piancatelli rearrangement Tandem Stereochemistry Chemistry Organic Chemistry General Chemistry Chemical Engineering automated sampling homogeneous catalysis Combinatorial chemistry Catalysis Inorganic Chemistry reaction mechanisms transient intermediate tracking Cascade reaction tandem reaction progress analysis cascade rearrangement Cancer Piancatelli rearrangement |
| Zdroj: | ACS Catalysis, vol 5, iss 8 Chung, R; Yu, D; Thai, VT; Jones, AF; Veits, GK; Read De Alaniz, J; et al.(2015). Tandem Reaction Progress Analysis as a Means for Dissecting Catalytic Reactions: Application to the Aza-Piancatelli Rearrangement. ACS Catalysis, 5(8), 4579-4585. doi: 10.1021/acscatal.5b01087. UC Santa Barbara: Retrieved from: http://www.escholarship.org/uc/item/892067f4 |
| ISSN: | 2155-5435 |
| Popis: | © 2015 American Chemical Society. Continuing developments in the elucidation techniques of complex catalytic processes is of foremost importance to modern synthetic chemistry, and the identification of efficient synthetic techniques relies on precise, reliable, and adaptable methods to dissect the mechanism of a given transformation. Currently, methods of reaction development are grounded upon the systematic modification of specific variables - such as temperature, time, concentration, etc. - to account for and control the dynamic series of coupled equilibria within a catalytic environment. On the other hand, tandem reaction analytical methods that involve the concomitant use of different instruments to probe a reaction can provide time-resolved information regarding active chemical species and facilitate the interrogation and optimization of the system. Herein, we report our study applying tandem in situ ReactIR and HPLC-MS monitoring to the dysprosium(III) triflate-catalyzed aza-Piancatelli rearrangement of 2-furylcarbinols, a reaction that grants access to trans-4,5-disubstituted cyclopentenones - common motifs in important biologically relevant and natural compounds. With a prototype automated sampling apparatus, information was obtained about the intrinsic chemoselectivity of the reaction, and previously unseen intermediates were observed, allowing for a more detailed reaction mechanism to be substantiated. The advantages of applying this type of tandem measurement to study these types of systems are also discussed. (Figure Presented). |
| Databáze: | OpenAIRE |
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