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Issue 29, 2019
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Hypercoordinate iodine for catalytic asymmetric diamination of styrene: insights into the mechanism, role of solvent, and stereoinduction

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Abstract

Hypercoordinate iodine has evolved as an impressive class of catalysts for various organic transformations. Extension of this idea to asymmetric applications, such as in the asymmetric difunctionalization of styrene or its derivatives, constitutes an important reaction. In this study, the mechanism and origin of stereoinduction in styrene diamination, with a sulfonimide (HNMs2) as the diaminating agent and iodoresorcinol (((iPr)2N(CO)-CH(Me)-O)2Ar–I) based chiral hypercoordinate iodine as the catalyst, are investigated using density functional theory calculations. The energetically preferred catalytic pathway has been found to involve, among other steps, two very important mechanistic events: (a) the formation of a catalyst–substrate complex by the action of styrene on the catalyst ArI(NMs2)2, resulting in the displacement of one of the imidates (NMs2); and (b) a rebound of the departed imidate on the iodine-bound styrene to form an iodonium ion intermediate with a N–C bond. Explicit interaction of the imidate ion with hexafluoroisopropanol (HFIP), used as a solvent additive, lowers the barrier for the formation of the iodonium ion. The P helical fold of the chiral arms of the iodoresorcinol catalyst is found to offer a chiral environment for the reactants. Coordination of the iodine catalyst to the styrene double bond is found to make the benzylic carbon more electrophilic and hence makes it the preferred site for the nucleophilic addition. In the chiral environment of the catalyst, an enhanced polarization of the styrene double bond is noticed when the double bond coordinates through the si prochiral face than the re face. Nucleophilic addition on the re face of the catalyst–substrate complex is associated with a lower activation barrier leading to the experimentally observed S enantiomeric product. The stereoselective model developed in this study can be employed to related asymmetric styrene difunctionalizations using similar hypercoordinate iodine catalysts.

Graphical abstract: Hypercoordinate iodine for catalytic asymmetric diamination of styrene: insights into the mechanism, role of solvent, and stereoinduction

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Publication details

The article was received on 27 Mar 2019, accepted on 07 Jun 2019 and first published on 10 Jun 2019


Article type: Edge Article
DOI: 10.1039/C9SC01513B
Chem. Sci., 2019,10, 7082-7090
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Hypercoordinate iodine for catalytic asymmetric diamination of styrene: insights into the mechanism, role of solvent, and stereoinduction

    A. Sreenithya, C. M. Hadad and R. B. Sunoj, Chem. Sci., 2019, 10, 7082
    DOI: 10.1039/C9SC01513B

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