Journal
SYNLETT
Volume 29, Issue 10, Pages 1257-1271Publisher
GEORG THIEME VERLAG KG
DOI: 10.1055/s-0036-1591579
Keywords
asymmetric synthesis; halogenations; electrophilic addition; alkenes; desymmetrization; heterocycles
Categories
Funding
- JSPS KAKENHI [16H05077, 16K18848]
- MEXT, Japan
- Japan Agency for Medical Research and Development (AMED)
- Grants-in-Aid for Scientific Research [16H05077, 16K18848] Funding Source: KAKEN
Ask authors/readers for more resources
Halocyclization of alkenes is commonly employed to increase molecular complexity during organic synthesis because it enables double installation of heteroatoms on a carbon-carbon double bond. Moreover, stereodefined halogenated compounds are widely found among naturally occurring compounds and can serve as versatile chiral building blocks. Therefore, the development of asymmetric halocyclization reactions is of great interest and, in recent years, there has been remarkable progress in catalytic asymmetric halogenation reactions. This account summarizes recent progress made by our group on phosphorus-catalyzed enantioselective bromocyclization of allylic amides. Building on a comprehensive study of the reaction mechanism, we discovered an intriguing catalytic reaction in which P+Br species serves as a fine-tuning element for substrate fixation. We also describe the application of this bromocyclization to asymmetric desymmetrization of 1,4-diene substrates and a concise synthesis of the HIV-protease inhibitor nelfinavir using the newly developed desymmetrization reaction as a key step. 1 Introduction 2 Enantioselective Bromocyclization of Allylic Amides with a BINAP Catalyst 2.1 Bromocyclization with a P/P Catalyst 2.2 Bromocyclization with a P/P=O Catalyst 3 Desymmetrization of Bisallylic Amides through Enantioselective Bromocyclization 3.1 Desymmetrization of Bisallylic Amides 3.2 Enantioselective Synthesis of Nelfinavir 4 Summary
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available