![Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F51444.jpg&w=3840&q=50)
A Remarkable Catalyst-Free Photochemical Alkene Hydrophosphination with Bis(trimethylsilyl)phosphonite
Eloïse Bréger1,2, Jade Dussart-Gautheret1, Rachid Taakili1,2
1Institut de Chimie de Nice, UMR7272, Université Côte d'Azur, Nice 06103, France.
Abstract:
This publication delves into a comprehensive exploration of a new synthetic route to functionalized phosphorus-derived compounds. Bis-(trimethylsilyl)-phosphonite HP-(OSiMe3)2, prepared in a high yield from H3PO2, was found to be an excellent reagent for hydrophosphination of activated, unactivated, and amino acid-derived olefins under UV irradiation and catalyst-, solvent- and glovebox-free conditions. The resulting phosphorus trivalent compounds have been subjected to postfunctionalization, leading to the formation of H-phosphinate, phosphonate, and thiophosphonate end products in good to excellent yields. With a combination of experimental and theoretical calculations, the mechanism for this hydrophosphination reaction has been investigated, revealing a radical process.
Related Concept Videos
02:24Reduction 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.
03:08Hydroboration-Oxidation of Alkenes
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...
02:47Alkynes 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.
01:14Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character, phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...