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Active template rotaxane synthesis through the Ni-catalyzed cross-coupling of alkylzinc reagents with redox-active esters

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Abstract

The synthesis of unsymmetrical axle [2]rotaxanes through a recently developed Ni-catalyzed C(sp3)–C(sp3) cross-coupling of redox-active esters (formed directly from carboxylic acids) and organozinc reagents (derived from alkyl bromides) is reported. The method also furnishes, as a minor product, the symmetrical axle [2]rotaxanes resulting from the homo-coupling of the organozinc half-thread. The rotaxanes are formed in up to 56% yield with the ratio of unsymmetrical rotaxane increasing with the cavity size of the macrocycle. In the absence of the redox-active ester neither rotaxane is formed, even though the homo-coupling rotaxane product does not incorporate the redox-active ester building block. A Ni(III) intermediate is consistent with these observations, providing support for the previously postulated mechanism of the Ni-catalyzed cross-coupling reaction.

Graphical abstract: Active template rotaxane synthesis through the Ni-catalyzed cross-coupling of alkylzinc reagents with redox-active esters

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Publication details

The article was received on 18 May 2019, accepted on 15 Jun 2019 and first published on 19 Jun 2019


Article type: Edge Article
DOI: 10.1039/C9SC02457C
Chem. Sci., 2019, Advance Article
  • Open access: Creative Commons BY license
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    Active template rotaxane synthesis through the Ni-catalyzed cross-coupling of alkylzinc reagents with redox-active esters

    J. Echavarren, M. A. Y. Gall, A. Haertsch, D. A. Leigh, V. Marcos and D. J. Tetlow, Chem. Sci., 2019, Advance Article , DOI: 10.1039/C9SC02457C

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