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Indium(0)‐Mediated C sp 3 –S/O Cross‐Coupling Approach Towards the Regioselective Alkylation of α‐Enolic Esters/Dithioesters: A Mechanistic Insight
Author(s) -
Chowdhury Sushobhan,
Chanda Tanmoy,
Gupta Ashutosh,
Koley Suvajit,
Ramulu B. Janaki,
Jones Raymond C. F.,
Singh Maya Shankar
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201301788
Subject(s) - regioselectivity , chemistry , alkylation , nucleophile , indium , selectivity , catalysis , coupling (piping) , coupling reaction , combinatorial chemistry , medicinal chemistry , computational chemistry , organic chemistry , mechanical engineering , engineering
We have reported an indium(0)‐mediated C sp 3–S/O cross‐coupling approach that leads to the highly regioselective alkylation of α‐enolic acetate/dithioacetate systems. This hetero cross‐coupling reaction does not require additional co‐catalyst or promoter, and the in situ generated organoindium species promotes the reaction by acting as the coupling partner of the α‐enolic acetate/dithioacetate substrates. The excellent selectivity for C ‐, S ‐, or O ‐alkylation is solely dependent on the nucleophilic behavior of α‐enolic acetate/dithioacetate systems. These results were further supported by DFT calculations of the relative electronic energies of the substrates and products as well as the activation barriers of the respective transformations.