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Remote Nucleophilic Allylation by Allylrhodium Chain Walking
Alistair Groves1,2, Jose I Martínez2, Joshua J Smith2
1The GlaxoSmithKline Carbon Neutral Laboratories for Sustainable, Chemistry, University of Nottingham, Jubilee Campus, Triumph Road, Nottingham, NG7 2TU, UK.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 15, 2018
Summary
Allylrhodium species migrate along carbon chains, enabling remote functionalization of esters, amides, and arenes. This chain walking reaction provides access to valuable Z-homoallylic alcohols and amines.
Area of Science:
- Organometallic Chemistry
- Organic Synthesis
- Catalysis
Background:
- Metal migration along carbon chains is key for remote functionalization.
- Existing methods primarily involve alkylmetal species, limiting scope.
- Allylmetal species offer potential for novel migration pathways.
Purpose of the Study:
- To investigate the chain walking of allylrhodium species.
- To explore remote functionalization using allylrhodium intermediates.
- To develop new synthetic routes to Z-homoallylic alcohols and amines.
Main Methods:
- Hydrorhodation of 1,3-dienes to form allylrhodium species.
- Observation of allylrhodium chain walking toward various functional groups.
- Nucleophilic allylation of aldehydes and imines with the functionalized allylrhodium species.
Main Results:
- Allylrhodium species were observed to undergo chain walking up to eight methylene units.
- Migration occurred towards esters, amides, and (hetero)arenes.
- The resulting conjugated species efficiently yielded Z-homoallylic alcohols and amines via allylation.
Conclusions:
- Allylrhodium chain walking provides a novel method for remote functionalization.
- This pathway expands the utility of allylmetal species in organic synthesis.
- The method offers a direct route to valuable Z-homoallylic products.
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