Decarboxylative Arylations in Natural Product Synthesis and Transfer Hydrofunctionalizations Using Cyclohexadienes
Final Report Abstract
A Ni-catalyzed alkene transfer hydrofunctionalization using readily prepared cyclohexadi-2,5-en-1-carbonitriles as HCN-donors was developed. In contrast to the previously disclosed Pd-catalyzed process with the same HCN-donors, a Lewis acid cocatalyst is not required. Furthermore, the Ni-process delivers internal (branched) nitriles as the products with excellent regioselectivity, whereas the Pd-catalyzed hydrocyanation provides linear nitriles. We also developed a novel process for the alkene hydration using Fe-catalysis with electron-poor nitroalkenes as oxidants in combination with silanes as reductants. While the intermolecular variant of this radical hydration provides high diastereoselectivity only for rigid alkenes, the corresponding intramolecular oxygen transfer occurs with high diastereoselectivity also on flexible alkenes. In these cases, the nitroarene moiety is covalently bound to the alkene acceptor. We also developed Fe-catalyzed alkene hydroalkynylation and hydroazidation reactions. Finally, we found that 2-substituted alkynyl sulfonyl fluorides are highly efficient radical fluorosulfonyl alkynylation reagents for the preparation of β-alkynylfluorosulfonylalkanes. The product fluorosulfones can be further diversified through SuFEX click reactions.
Publications
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Nickel-Catalyzed Markovnikov Transfer Hydrocyanation in the Absence of Lewis Acid. Organic Letters, 22(11), 4456-4460.
Frye, Nils L.; Bhunia, Anup & Studer, Armido
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Fe‐Catalyzed Anaerobic Mukaiyama‐Type Hydration of Alkenes using Nitroarenes. Angewandte Chemie International Edition, 60(15), 8313-8320.
Bhunia, Anup; Bergander, Klaus; Daniliuc, Constantin Gabriel & Studer, Armido
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Recent advances in radical chemistry proceeding through pro-aromatic radicals. Chem, 7(8), 2060-2100.
Bhunia, Anup & Studer, Armido
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Radical 1‐Fluorosulfonyl‐2‐alkynylation of Unactivated Alkenes. Angewandte Chemie International Edition, 61(12).
Frye, Nils Lennart; Daniliuc, Constantin G. & Studer, Armido
