Stereodivergent atom transfer radical addition of α-functionalized alkyl iodides to alkynes: a strategy for selective synthesis of both E - and Z -iodoalkenes

The geometrical control of atom transfer radical addition (ATRA) reactions to alkynes poses significant challenges. Herein, we present a uniform solution by developing a stereodivergent synthetic method for both isomers of the resulting alkene products, starting from the same materials. The synthesi...

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Bibliographic Details
Published in:Chemical communications (Cambridge, England) England), 2024-11, Vol.60 (90), p.13251-13254
Main Authors: Tang, Ya-Jie, Fan, Qi, Li, Xiaoya, Li, Qingjiang, Yin, Biaolin, Wang, Honggen
Format: Article
Language:English
Subjects:
Alkynes
Chemical reactions
Chemical synthesis
Functional groups
Iodides
Isomers
Manganese
Radicals
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Summary:The geometrical control of atom transfer radical addition (ATRA) reactions to alkynes poses significant challenges. Herein, we present a uniform solution by developing a stereodivergent synthetic method for both isomers of the resulting alkene products, starting from the same materials. The synthesis of the thermodynamically more stable isomer utilizes the strategy of uphill catalysis while the accumulation of the less stable isomer is facilitated by a manganese-catalyzed iodo-abstraction/radical rebound process, taking advantage of its reversibility. Various substituted alkyl iodides can be used to provide easy access to both isomers of iodoalkene products with valuable functional groups such as CF , CF H, CN, ester, or amide at the allylic position.
ISSN:1359-7345
1364-548X
1364-548X
DOI:10.1039/d4cc04948a