Asymmetric Total Syntheses of Di‐ and Sesquiterpenoids by Catalytic C−C Activation of Cyclopentanones
| Autor: | Adriana Y. Prichina, Si-Hua Hou, Guangbin Dong, Mengxi Zhang |
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| Rok vydání: | 2020 |
| Předmět: |
Allylic rearrangement
010405 organic chemistry Chemistry Stereochemistry Enantioselective synthesis Regioselectivity Total synthesis Chemistry Techniques Synthetic Cyclopentanes General Chemistry General Medicine 010402 general chemistry Cyclopentanone 01 natural sciences Article Catalysis 0104 chemical sciences chemistry.chemical_compound Tetralone Rhodium Hydrogenation Sesquiterpenes Amination |
| Zdroj: | Angew Chem Int Ed Engl |
| ISSN: | 1521-3757 0044-8249 |
| DOI: | 10.1002/ange.201915821 |
| Popis: | To show the synthetic utility of the catalytic C-C activation of less strained substrates, described here are the collective and concise syntheses of the natural products (-)-microthecaline A, (-)-leubehanol, (+)-pseudopteroxazole, (+)-seco-pseudopteroxazole, pseudopterosin A-F and G-J aglycones, and (+)-heritonin. The key step in these syntheses involve a Rh-catalyzed C-C/C-H activation cascade of 3-arylcyclopentanones, which provides a rapid and enantioselective route to access the polysubstituted tetrahydronaphthalene cores presented in these natural products. Other important features include 1) the direct C-H amination of the tetralone substrate in the synthesis of (-)-microthecaline A, 2) the use of phosphoric acid to enhance efficiency and regioselectivity for problematic cyclopentanone substrates in the C-C activation reactions, and 3) the direct conversion of serrulatane into amphilectane diterpenes by an allylic cyclodehydrogenation coupling. |
| Databáze: | OpenAIRE |
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