Template-Assisted meta-C−H Alkylation and Alkenylation of Arenes
Sukdev Bag
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorDr. Ramasamy Jayarajan
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Department of Biosciences and Bioengineering, Indian Institute of Technology Bombay, India
Search for more papers by this authorRahul Mondal
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorCorresponding Author
Prof. Dr. Debabrata Maiti
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorSukdev Bag
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorDr. Ramasamy Jayarajan
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Department of Biosciences and Bioengineering, Indian Institute of Technology Bombay, India
Search for more papers by this authorRahul Mondal
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorCorresponding Author
Prof. Dr. Debabrata Maiti
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076 India
Search for more papers by this authorGraphical Abstract
On target: Pyrimidine-based, template-assisted meta-C−H alkylation and alkenylation with allyl alcohols and protected allyl alcohols has been developed. Sulfonyl, carbonyl, and phosphonyl esters were used as linkers between the directing group (DG) and target meta-C−H bond of arenes.
Abstract
To expand the scope of meta-functionalization, a pyrimidine-based template effective for the formation of β-aryl aldehydes and ketones, using allyl alcohols, by meta-C−H activation of benzylsulfonyl esters is described. In addition, α,β-unsaturated aldehydes were generated by in situ olefination and deprotection of allyl benzyl ethers. These new functionalizations at the meta-position of an arene have also been successfully implemented in benzylphosphonate, phenethyl carbonyl, and phenethylsulfonyl ester scaffolds. Key to these successful new functionalizations is the creation of an electropositive palladium center by accepting the electron cloud from the metal to the energetically low-lying π-orbitals of pyrimidine ring, and it favors coordination of allyl alcohol to the metal center.
Supporting Information
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