Enantioselective Catalytic Aldehyde α-Alkylation/Semipinacol Rearrangement: Construction of α-Quaternary-δ-Carbonyl Cycloketones and Total Synthesis of (+)-Cerapicol
| Autor: | Fu-Min Zhang, Xiao-Ming Zhang, Hong Wang, Zhen Li, Yong-Qiang Tu, Xi-Chao Wang, Jie Yang, Shao-Hua Wang |
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| Rok vydání: | 2020 |
| Předmět: |
chemistry.chemical_classification
Allylic rearrangement 010405 organic chemistry Alkene Enantioselective synthesis food and beverages General Chemistry 010402 general chemistry 01 natural sciences Aldehyde Catalysis 0104 chemical sciences Enamine Semipinacol rearrangement chemistry.chemical_compound chemistry Organocatalysis Cyclopropanol Organic chemistry |
| Zdroj: | Angewandte Chemie (International ed. in English). 59(22) |
| ISSN: | 1521-3773 |
| Popis: | An enantioselective aldehyde α-alkylation/semipinacol rearrangement was achieved through organo-SOMO catalysis. The catalytically generated enamine radical cation serves as a carbon radical electrophile that can stereoselectively add to the alkene of an allylic alcohol and initiate ensuing ring-expansion of cyclopropanol or cyclobutanol. This tandem reaction enables the production of a wide range of nonracemic functionalizable α-quaternary-δ-carbonyl cycloketones in high yields and excellent enantioselectivity from simple aldehydes and allylic alcohols. As a key step, the intramolecular reaction was also successfully applied in the asymmetric total synthesis of (+)-cerapicol. |
| Databáze: | OpenAIRE |
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