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Constructing Thioether/Vinyl Sulfide-tethered Helical Peptides Via Photo-induced Thiol-ene/yne Hydrothiolation
Published on: August 1, 2018
Strain Meets Sulfur: Click Hydrothiolation of Cyclic Alkynes with In Situ Generated Dithiocarbamic Acids
Azim Ziyaei Halimehjani1, Parisa Yaqubnezhad Pazoki1, Aleksandra A Vidyakina2
1Department of Chemistry, Sharif University of Technology, Tehran 11155-9516, Iran.
None:
A robust strategy for the hydrothiolation of heterocycloalkynes with in situ generated dithiocarbamic acids, "Strain-Promoted diThiocarbamic acid-Alkyne Click" (SPTAC), was developed and successfully extended to diverse cycloalkynes and a wide range of amines and their hydrochlorides, affording hydrothiolation adducts in high to excellent yields. DFT calculations revealed a concerted pseudopericyclic mechanism of SPTAC. The thiol-yne click transformation provides a versatile platform for the construction of functional sulfur-containing molecules for various applications.
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Alkynes to Aldehydes and Ketones: Acid-Catalyzed Hydration
Analogous to alkenes, alkynes also undergo acid-catalyzed hydration. While the addition of water to an alkene gives an alcohol, hydration of alkynes produces different products such as aldehydes and ketones.
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.
Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.
Acid Halides to Carboxylic Acids: Hydrolysis
As shown below, the mechanism involves a nucleophilic attack by water at the carbonyl carbon to form a tetrahedral intermediate. This is followed by the reformation of the carbon–oxygen π bond along with the departure of a halide ion. A final proton transfer step yields...
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