Azaborine benzylic ion stability and reactivity in ionic polymerization. Issue 7 (3rd February 2022)

• Record Type: Journal Article
• Authors: Wakefield IV, Herbert; Jiang, Qifeng; Klausen, Rebekka S.
• Is Part Of: Organic & biomolecular chemistry. Volume 20:Issue 7(2022)
• Page Start: 1407
• Page End: 1414
• Publication Date: 2022-02-03
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d1ob02467a
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : The reactivity of BN 2-vinylnaphthalene with ionic polymerization iniatiors was investigated. Aromatic functionalization was observed instead of polymerization. Calculations indicate the effect of BN isosterism on the stability of benzylic ions. Abstract : Benzylic cations and anions are implicated in the mechanism of critical organic transformations, such as styrene polymerization. We investigate the influence of BN for CC bond substitution on the reactivity of benzylic ions and the effect on BN 2-vinylnaphthalene (BN2VN) ionic polymerization. Calculations suggest that the proximity of a N donor to a cation influences the stability of a BN benzylic cation, rationalizing unsuccessful protonation of BN2VN. Organolithium reagents undergo clean nucleophilic aromatic substitution with BN2VN and related BN naphthalenes via a hypothesized associative mechanism. These results suggest design principles for main group aromatic substitution.