Lanthanide triflate-catalyzed arene acylation. Relation to classical Friedel-Crafts acylation

Alma Dzudza, Tobin J Marks

Research output: Contribution to journalArticle

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Abstract

(Chemical Equation Presented) Lanthanide trifluoromethanesulfonates, Ln(OTf)3 (OTf- = trifluoromethanesulfonate), serve as effective precatalysts for the rapid, regioselective, intermolecular acylation of activated arenes. This contribution probes mechanism and metal ionic radius effects in the catalytic lanthanide triflate-mediated acylation of anisole with acetic anhydride. Kinetic studies of Ln(OTf)3 (Ln = La, Eu, Yb, Lu)-mediated anisole acylation with acetic anhydride in nitromethane reveal the rate law ν ∼ k3 [Ln3+]1[acetic anhydride]1[anisole]1. Eyring and Arrhenius analyses yield ΔH‡ = 12.9 (4) kcal·mol-1, ΔS‡ = -44.8 (1.3) e.u., and Ea = 13.1 (4) kcal·mol-1 for Ln = Yb, with the negative ΔS‡ implying a highly organized transition state. The observed primary kinetic isotope effect of k H/kD = 2.6 ± 0.15 is consistent with arene C-H bond scission in the turnover-limiting step. The proposed catalytic pathway involves precatalyst formation via interaction of Ln(OTf)3 with acetic anhydride, followed by Ln3+-anisole π-complexation, substrate-electrophile σ-complex formation, and turnover-limiting C-H bond scission. Lanthanide size effects on turnover frequencies are consistent with a transition state lacking significant ionic radius-dependent steric constraints. Substrate-Ln3+ interactions using paramagnetic Gd3+ and Yb3+ NMR probes and factors affecting reaction rates such as arene substituent and added LiClO4 cocatalyst are also explored.

Original languageEnglish
Pages (from-to)4004-4016
Number of pages13
JournalJournal of Organic Chemistry
Volume73
Issue number11
DOIs
Publication statusPublished - Jun 6 2008

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Acylation
Lanthanoid Series Elements
Kinetics
Substrates
Complexation
Isotopes
Reaction rates
Metals
Nuclear magnetic resonance
acetic anhydride
anisole
trifluoromethanesulfonic acid

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Lanthanide triflate-catalyzed arene acylation. Relation to classical Friedel-Crafts acylation. / Dzudza, Alma; Marks, Tobin J.

In: Journal of Organic Chemistry, Vol. 73, No. 11, 06.06.2008, p. 4004-4016.

Research output: Contribution to journalArticle

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