Ortho-Carborane-Supported Hypervalent Iodine(III) Reagents: A Scaffold for Enhanced Oxidative Capability
Marcus Sceney1, Keith F White1, Jason L Dutton1
1Department of Biochemistry and Chemistry, La Trobe Institute for Molecular Science, La Trobe University, Melbourne, 3086, Victoria, Australia.
None:
The first C-bound ortho-carborane (oCb) supported hypervalent iodine(III) -IL2 type species are reported in RoCb-IL2, for L = F and OTf, including two structurally verified -IF2 examples. Initial synthetic observations and supporting theoretical calculations suggest that the new oCb-IL2 type compounds will be more reactive than any known Ar-IL2 compound. This is exemplified by a previously unobserved oxidative demethylation of trimethylsilyl fluoride, suggesting that many substrates unreactive toward Ar-IL2 could be susceptible to oxidation by oCb-IL2.
More Related Videos
12:27Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes
Published on: September 8, 2013
06:34Synthesis of Antiviral Tetrahydrocarbazole Derivatives by Photochemical and Acid-catalyzed C-H Functionalization via Intermediate Peroxides CHIPS
Published on: June 20, 2014
Related Concept Videos
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Radical Substitution: Hydrogenolysis of Alkyl Halides with Tributyltin Hydride
The bonds formed in this reaction are stronger than the bonds broken, making it energetically favorable. The reaction follows a radical chain mechanism similar to radical halogenation...
α-Bromination of Carboxylic Acids: Hell–Volhard–Zelinski Reaction
Regioselectivity of Electrophilic Additions-Peroxide Effect
Regioselectivity and Stereochemistry of Hydroboration
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn...
