Rationally Designing Regiodivergent Dipolar Cycloadditions: Frontier Orbitals Show How To Switch between [5+3] and [4+2] Cycloadditions

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A pyridinium zwitterion substrate is employed with two different types of transition metal catalysts to develop a regiodivergent cycloaddition. The pyridinium zwitterion is a highly reactive dipolar substrate that can undergo a dipolar cycloaddition with various reactants. It has multiple reaction sites, and the chemoselectivity is determined by the electronic demand of the catalyst substrate complex. The reaction with nucleophilic Pd reagents affords fused N-heterocyclic compounds via regioselective [4 + 2] cycloaddition. The origin of the site selectivity and the mechanism of this reaction are investigated in this combined experimental and computational study. We found that the pyridinium zwitterion plays a completely different role in the palladium(0)-catalyzed [4 + 2] cycloaddition reaction and in the rhodium(II)-catalyzed [5 + 3] cycloaddition, which was examined experimentally in a previous study. The frontier molecular orbitals of the pyridinium substrate and activated catalyst complex reveal that the pyridinium zwitterion can act as both a nucleophile and an electrophile depending on the reaction partner in a manner much more defined than that of conventional substrates, leading to the observed regiodivergent chemical reactivity.
Publisher
AMER CHEMICAL SOC
Issue Date
2018-07
Language
English
Article Type
Article
Keywords

EFFECTIVE CORE POTENTIALS; SOLVATION FREE-ENERGIES; MOLECULAR CALCULATIONS; METALLACYCLE INTERMEDIATE; METAL; VINYLCYCLOPROPANES; MECHANISM; DENSITY; HYDROGEN; ALKYNES

Citation

ACS CATALYSIS, v.8, no.7, pp.6353 - 6361

ISSN
2155-5435
DOI
10.1021/acscatal.8b00845
URI
http://hdl.handle.net/10203/244979
Appears in Collection
CH-Journal Papers(저널논문)
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