Homo- Versus Hetero- [2+2+2] Rhodium-Catalyzed Cycloaddition: Effect of a Self-Assembled Capsule on the Catalytic Outcome
Maxime Steinmetz, David Sémeril
TL;DR
A self-assembled capsule changes the outcome of a rhodium-catalyzed chemical reaction by favoring different products.
Contribution
A supramolecular capsule is shown to invert the selectivity of [2+2+2] cycloaddition reactions.
Findings
Without the capsule, homocycloaddition products dominate.
With the capsule, heterocycloaddition products form in 53–69% yield.
Abstract
The cationic chloro-P-{[4-(diphenylphosphanyl)phenyl]-N,N-dimethylmethanammonio(norbornadiene)rhodium(I) complex was encapsulated inside a self-assembled hexameric capsule. This capsule was obtained through a reaction involving 2,8,14,20-tetra-undecyl-resorcin[4]arene and water in chloroform. The formation of an inclusion complex was deduced from a combination of spectral measurements (UV-visible spectroscopy, 1H, 31P{1H} NMR and DOSY). The rhodium complex was evaluated in the [2+2+2] cycloaddition between N,N-dipropargyl-p-toluenesulfonamide and arylacetylene derivatives. In the presence of two equivalents of arylacetylenes in water-saturated chloroform at 60 °C for 24 h, the 4-methyl-N-(prop-2-yn-1-yl)-N-((2-tosylisoindolin-5-yl)methyl)benzenesulfonamide, the homocycloaddition product of 1,6-diyne is predominantly formed. In the presence of the supramolecular capsule, a selectivity…
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Taxonomy
TopicsOrganometallic Complex Synthesis and Catalysis · Asymmetric Hydrogenation and Catalysis · Catalytic Alkyne Reactions