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Synthesis, Structure, and Reactivity of 5-(Aryl)dibenzothiophenium Triflates.

ABSTRACT: A synthetic protocol for the preparation of 5-(aryl)dibenzothiophenium salts starting from inexpensive dibenzothiophene S-oxide and simple arenes is reported. The scope of the method regarding the nature of the arene is evaluated, intermediates along the reaction sequence have been trapped, and side-reactions identified. In addition, the X-ray structures of a complete set of these salts are reported and their reactivities studied. Specifically, chemoselective Suzuki coupling is observed at the dibenzothiophenium in the presence of iodides.

SUBMITTER: Kafuta K

PROVIDER: S-EPMC7004049 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Synthesis, Structure, and Reactivity of 5-(Aryl)dibenzothiophenium Triflates.

Kafuta Kevin K Korzun André A Böhm Marvin M Golz Christopher C Alcarazo Manuel M

Angewandte Chemie (International ed. in English) 20191126 5

A synthetic protocol for the preparation of 5-(aryl)dibenzothiophenium salts starting from inexpensive dibenzothiophene S-oxide and simple arenes is reported. The scope of the method regarding the nature of the arene is evaluated, intermediates along the reaction sequence have been trapped, and side-reactions identified. In addition, the X-ray structures of a complete set of these salts are reported and their reactivities studied. Specifically, chemoselective Suzuki coupling is observed at the d ...[more]

PMID: 31680351

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Project description:The advent of transition-metal catalysed strategies for forming new carbon-carbon bonds has revolutionized the field of organic chemistry, enabling the efficient synthesis of ligands, materials, and biologically active molecules. In cases where a single metal fails to promote a selective or efficient transformation, the synergistic cooperation of two distinct catalysts--multimetallic catalysis--can be used instead. Many important reactions rely on multimetallic catalysis, such as the Wacker oxidation of olefins and the Sonogashira coupling of alkynes with aryl halides, but this approach has largely been limited to the use of metals with distinct reactivities, with only one metal catalyst undergoing oxidative addition. Here, we demonstrate that cooperativity between two group 10 metal catalysts--(bipyridine)nickel and (1,3-bis(diphenylphosphino)propane)palladium--enables a general cross-Ullmann reaction (the cross-coupling of two different aryl electrophiles). Our method couples aryl bromides with aryl triflates directly, eliminating the use of arylmetal reagents and avoiding the challenge of differentiating between multiple carbon-hydrogen bonds that is required for direct arylation methods. Selectivity can be achieved without an excess of either substrate and originates from the orthogonal reactivity of the two catalysts and the relative stability of the two arylmetal intermediates. While (1,3-bis(diphenylphosphino)propane)palladium reacts preferentially with aryl triflates to afford a persistent intermediate, (bipyridine)nickel reacts preferentially with aryl bromides to form a transient, reactive intermediate. Although each catalyst forms less than 5 per cent cross-coupled product in isolation, together they are able to achieve a yield of up to 94 per cent. Our results reveal a new method for the synthesis of biaryls, heteroaryls, and dienes, as well as a general mechanism for the selective transfer of ligands between two metal catalysts. We anticipate that this reaction will simplify the synthesis of pharmaceuticals, many of which are currently made with pre-formed organometallic reagents, and lead to the discovery of new multimetallic reactions.

Dataset Information

Synthesis, Structure, and Reactivity of 5-(Aryl)dibenzothiophenium Triflates.

Publications

Synthesis, Structure, and Reactivity of 5-(Aryl)dibenzothiophenium Triflates.

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