Iron-mediated C(sp3) transthioetherification
Yuanjie Yang1, Mingzhe Zhang1, Elias Picazo1
1Department of Chemistry, Loker Hydrocarbon Research Institute, University of Southern California, 837 Bloom Walk, Los Angeles, California 90089-1661, United States.
Abstract:
Thioethers and disulfides are two sulfur-based functional groups commonly found in essential macronutrients, enzymes, therapeutics, materials, and agrochemicals. The ability to readily exchange one sulfur-containing unit for another through a single transthioetherification process presents an opportunity for facile sulfur group exchange. Despite the importance of thioethers, methods for transthioetherification remain limited to sp2-hybridized thioethers. Herein, we report the C(sp3) transthioetherification of benzylic thioethers with disulfide reagents mediated by iron. In addition to an iron source, use of substoichiometric benzylic bromide enables the reaction to be performed at lower temperatures. The reaction is operable with substrates containing diverse functionality on both the carbon and disulfide coupling partners, and the final product concentration can be influenced with higher loadings of disulfide starting material.
Related Concept Videos
02:33Preparation and Reactions of Thiols
01:26Radical 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 reactions,...
01:17Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
02:04Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids
![[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F13097.jpg&w=3840&q=75)
01:24[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
03:00Preparation of Epoxides
Epoxides result from alkene oxidation, which can be achieved by a) air, b) peroxy acids, c) hypochlorous acids, and d) halohydrin cyclization.
Epoxidation with Peroxy Acids
Epoxidation of alkenes via oxidation with peroxy acids involves the conversion of a carbon–carbon double bond to an epoxide using the oxidizing agent meta-chloroperoxybenzoic acid, commonly known as MCPBA. Since the O–O bond of peroxy acids is very weak, the addition of electrophilic oxygen of peroxy acids to...