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Mechanism of the bis(imino)pyridine-iron-catalyzed hydromagnesiation of styrene derivatives
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Neate, Peter G. N., Greenhalgh, Mark D., Brennessel, William W., Thomas, Stephen P. and Neidig, Michael L. (2019) Mechanism of the bis(imino)pyridine-iron-catalyzed hydromagnesiation of styrene derivatives. Journal of the American Chemical Society, 141 (25). pp. 10099-10108. doi:10.1021/jacs.9b04869
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Official URL: https://pubs.acs.org/doi/abs/10.1021/jacs.9b04869
Abstract
Iron-catalyzed hydromagnesiation of styrene derivatives offers a rapid and efficient method to generate benzylic Grignard reagents, which can be applied in a range of transformations to provide products of formal hydrofunctionalization. While iron-catalyzed methodologies exist for the hydromagnesiation of terminal alkenes, internal alkynes, and styrene derivatives, the underlying mechanisms of catalysis remain largely undefined. To address this issue and determine the divergent reactivity from established cross-coupling and hydrofunctionalization reactions, a detailed study of the bis(imino)pyridine iron-catalyzed hydromagnesiation of styrene derivatives is reported. Using a combination of kinetic analysis, deuterium labeling, and reactivity studies as well as in situ Fe Mössbauer spectroscopy, key mechanistic features and species were established. A formally iron(0) ate complex [ BIPFe(Et)(CH═CH)] was identified as the principle resting state of the catalyst. Dissociation of ethene forms the catalytically active species which can reversibly coordinate the styrene derivative and mediate a direct and reversible β-hydride transfer, negating the necessity of a discrete iron hydride intermediate. Finally, displacement of the tridentate bis(imino)pyridine ligand over the course of the reaction results in the formation of a tris-styrene-coordinated iron(0) complex, which is also a competent catalyst for hydromagnesiation.
| Item Type: | Journal Article | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Subjects: | Q Science > QD Chemistry | ||||||||
| Divisions: | Faculty of Science > Chemistry | ||||||||
| Journal or Publication Title: | Journal of the American Chemical Society | ||||||||
| Publisher: | ACS Publications | ||||||||
| ISSN: | 1520-5126 | ||||||||
| Official Date: | 26 June 2019 | ||||||||
| Dates: |
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| Volume: | 141 | ||||||||
| Number: | 25 | ||||||||
| Page Range: | pp. 10099-10108 | ||||||||
| DOI: | 10.1021/jacs.9b04869 | ||||||||
| Status: | Peer Reviewed | ||||||||
| Publication Status: | Published | ||||||||
| Access rights to Published version: | Restricted or Subscription Access | ||||||||
| Funder: | National Institutes of Health, NSF | ||||||||
| Grant number: | R01 GM111480/GM/NIGMS NIH HHS/United States; NSF CHE-1725028 |
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