Issue 29, 2019

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

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

Supplementary files

Article information

Article type
Edge Article
Submitted
27 mrt 2019
Accepted
07 jun 2019
First published
10 jun 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2019,10, 7082-7090

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

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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