title: Template-Assisted meta-C-H Alkylation and Alkenylation 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.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076, India.
authors.forename: Sukdev
authors.initials: S
authors.lastname: Bag
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076, India.|Department of Biosciences and Bioengineering, Indian Institute of Technology Bombay, India.
authors.forename: Ramasamy
authors.initials: R
authors.lastname: Jayarajan
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076, India.
authors.forename: Rahul
authors.initials: R
authors.lastname: Mondal
authors.affiliation: Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai-, 400 076, India.
authors.forename: Debabrata
authors.initials: D
authors.lastname: Maiti
keywords: C−H activation; alkenylation; alkylation; arenes; palladium