Oxidative rearrangement of alkynes to chiral α-arylalkanoic esters
Rawiyah Alkahtani, Johannes Westphäling, Aleksandra Gorecka, Rasool Babaahmadi, Hanaa Gieman, Maylis Finance, Jaime Lorente-Martinez, Dhananjay Bhattacherjee, Rebecca L. Melen, Mu-Hyun Baik, Thomas Wirth
TL;DR
A new green method creates chiral esters from alkynes with high yield and selectivity using iodine reagents.
Contribution
A metal-free, enantioselective oxidative rearrangement of alkynes to chiral esters is developed with high yield and enantiomeric excess.
Findings
Chiral α-arylalkanoic esters are synthesized with up to 91% yield and 99% enantiomeric excess.
The reaction works well with electron-rich non-terminal arylalkynes under green conditions.
DFT calculations explain the origin of the enantioselectivity in the process.
Abstract
Chiral α-arylalkanoic esters, valued as anti-inflammatory agents, are synthesised through an enantioselective oxidative rearrangement of alkynes under green, metal-free conditions. This study achieves this transformation using chiral iodine(iii) reagents with para-toluenesulfonic acid and various alcohols, producing the esters in up to 91% yield and 99% enantiomeric excess. The scope of the reaction particularly includes electron-rich non-terminal arylalkynes. Density functional theory calculations give insight into the origin of enantioselectivities of this process. A green, metal-free method achieves enantioselective oxidative rearrangement of alkynes to chiral α-arylalkanoic esters, giving up to 91% yield and 99% ee. Chiral iodine(iii) reagents convert electron-rich arylalkynes, with DFT explaining the high selectivity.
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Taxonomy
TopicsCatalytic C–H Functionalization Methods · Oxidative Organic Chemistry Reactions · Vanadium and Halogenation Chemistry