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Synthesis of Macrocyclic Ketones through Catalyst-Free Electrophilic Halogen-Mediated Semipinacol Rearrangement: Application to the Total Synthesis of (±)-Muscone
Abstract
A series of macrocycles were successfully prepared using electrophilic halogen-mediated semipinacol rearrangement under mild conditions. Although the expansion from small ring to medium ring is an energetically unfavorable process, the electrophilic halogenation was found to be powerful enough to override such an energy barrier. The rearranged products could further undergo Dowd–Beckwith rearrangement to give the corresponding one-carbon ring-expanded ketones. This approach has been applied to the total synthesis of the natural product (±)-muscone, which is widely used in modern perfumery and medicines, in a two-step sequence- Text
- Journal contribution
- Biophysics
- Biochemistry
- Microbiology
- Genetics
- Biotechnology
- Evolutionary Biology
- Ecology
- Plant Biology
- Chemical Sciences not elsewhere classified
- Physical Sciences not elsewhere classified
- electrophilic halogen-mediated semipinacol rearrangement
- Macrocyclic Ketones
- energy barrier
- macrocycle
- sequence
- series
- muscone
- Application
- perfumery
- medium ring
- synthesis
- Catalyst-Free Electrophilic Halogen-Mediated Semipinacol Rearrangement
- electrophilic halogenation
- approach
- Total Synthesis
- Muscone
- one-carbon ring-expanded ketones
- Dowd