From Metallacycle-Mediated Annulative Cross-Coupling to Steroidal Tetracycles through Intramolecular C9–C10 Bond Formation
| العنوان: | From Metallacycle-Mediated Annulative Cross-Coupling to Steroidal Tetracycles through Intramolecular C9–C10 Bond Formation |
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| المؤلفون: | Chinmay P Bhatt, Adam B. Millham, Glenn C. Micalizio |
| المصدر: | Org Lett |
| بيانات النشر: | American Chemical Society (ACS), 2020. |
| سنة النشر: | 2020 |
| مصطلحات موضوعية: | Annulation, Molecular Structure, 010405 organic chemistry, Stereochemistry, Aryl, Organic Chemistry, Diastereomer, Stereoisomerism, Metallacycle, 010402 general chemistry, 01 natural sciences, Biochemistry, Semisynthesis, Article, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Cyclization, Heck reaction, Intramolecular force, Steroids, Physical and Theoretical Chemistry, Oxidation-Reduction |
| الوصف: | While semisynthesis is a common platform for medicinal investigation of steroidal systems, varying the nature of substitution and stereochemistry at C9 and C10 remains challenging. It is demonstrated here that de novo synthesis, enabled by a metallacycle-centered annulation reaction, provides a uniquely effective means of addressing this problem. In short, double asymmetric Friedel-Crafts cyclization proved most effective for establishing anti- relative stereochemistry (with respect to C13), while an intramolecular Heck reaction reliably delivered the syn- diastereomers with high selectivity. In addition, these studies reveal that this oxidative rearrangement is effective for establishing a C10 quaternary center boasting variable alkyl or aryl substitution. |
| تدمد: | 1523-7052 1523-7060 |
| DOI: | 10.1021/acs.orglett.0c02358 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::b4fce0291fbf805d5bb4cc16fec30f1d https://doi.org/10.1021/acs.orglett.0c02358 |
| Rights: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....b4fce0291fbf805d5bb4cc16fec30f1d |
| قاعدة البيانات: | OpenAIRE |
| تدمد: | 15237052 15237060 |
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| DOI: | 10.1021/acs.orglett.0c02358 |