H-bonded reusable template assisted para-selective ketonisation using soft electrophilic vinyl ethers
| Autor: | Giuseppe Zanoni, Massimo Brochetta, Peng Liu, Arun Maji, Debabrata Maiti, Gang Lu, Amit Dahiya, Trisha Bhattacharya |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2018 |
| Předmět: |
HECK REACTIONS
Bioactive molecules Science General Physics and Astronomy 010402 general chemistry 01 natural sciences General Biochemistry Genetics and Molecular Biology Article Acylation CARBENE CATALYZED SYNTHESIS ACTIVATION chemistry.chemical_compound Formal synthesis lcsh:Science OLEFINS COUPLING REACTIONS Multidisciplinary 010405 organic chemistry Substrate (chemistry) General Chemistry ACID DERIVATIVES Combinatorial chemistry CARBON NUCLEOPHILES 0104 chemical sciences TRANSIENT METALLACYCLES ACYLATION ALKYL-HALIDES chemistry Electrophile lcsh:Q Selectivity Protic solvent |
| Zdroj: | Nature Communications, Vol 9, Iss 1, Pp 1-10 (2018) Nature Communications |
| ISSN: | 2041-1723 |
| Popis: | In nature, enzymatic pathways generate Caryl−C(O) bonds in a site-selective fashion. Synthetically, Caryl−C(O) bonds are synthesised in organometallic reactions using prefunctionalized substrate materials. Electrophilic routes are largely limited to electron-rich systems, non-polar medium, and multiple product formations with a limited scope of general application. Herein we disclose a directed para-selective ketonisation technique of arenes, overriding electronic bias and structural congestion, in the presence of a polar protic solvent. The concept of hard–soft interaction along with in situ activation techniques is utilised to suppress the competitive routes. Mechanistic pathways are investigated both experimentally and computationally to establish the hypothesis. Synthetic utility of the protocol is highlighted in formal synthesis of drugs, drug cores, and bioactive molecules. Electrophilic acylation of arenes is largely limited to electron rich systems, non-polar medium and often displays moderate selectivity. Here, the authors show a directed para-selective ketonisation of arenes, overriding electronic bias and structural congestion, and apply it to the synthesis of bioactive compounds. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|