One and Two-Carbon Homologation of Primary and Secondary Alcohols to Corresponding Carboxylic Esters Using β-Carbonyl BT Sulfones as a Common Intermediate
| Autor: | Ondřej Kováč, David J.-Y.D. Bon, Vendula Ferugová, František Zálešák, Jiri Pospisil |
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| Rok vydání: | 2018 |
| Předmět: |
Primary (chemistry)
010405 organic chemistry Chemistry Organic Chemistry Substrate (chemistry) chemistry.chemical_element Alkylation 010402 general chemistry 01 natural sciences 0104 chemical sciences Sulfone chemistry.chemical_compound Nucleophile Benzothiazole Organic chemistry Mitsunobu reaction Carbon |
| Zdroj: | The Journal of organic chemistry. 83(9) |
| ISSN: | 1520-6904 |
| Popis: | Herein we report the efficient one- and two-carbon homologation of 1° and 2° alcohols to their corresponding homologated esters via the Mitsunobu reaction using β-carbonyl benzothiazole (BT) sulfone intermediates. The one-carbon homologation approach uses standard Mitsunobu C–S bond formation, oxidation and subsequent alkylation, while the two-carbon homologation uses a less common C–C bond forming Mitsunobu reaction. In this latter case, the use of β-BT sulfone bearing esters lowers the pKa sufficiently enough for the substrate to be used as a carbon-based nucleophile and deliver the homologated β-BT sulfone ester, and this superfluous sulfone group can then be cleaved. In this paper we describe several methods for the effective desulfonylation of BT sulfones and have developed methodology for one-pot alkylation-desulfonylation sequences. As such, overall, a one-carbon homologation sequence can be achieved in a two-pot (four step) procedure and the two-carbon homologation in a two-pot (three step) proced... |
| Databáze: | OpenAIRE |
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