65690-99-5

Upstream product

• 5908-41-8 benzoyltrimethylsilane 
• 22966-22-9 (E)-1-(4-chlorophenyl)-3-phenyl-2-propen-1-one 
• 100-42-5 styrene 
• 100-52-7 benzaldehyde 
• 3923-51-1 1,1-diphenylprop-2-en-1-ol 
• 104-88-1 4-chlorobenzaldehyde 

Relevant academic research and scientific papers

N-Heterocyclic Carbene-Photocatalyzed Tricomponent Regioselective 1,2-Diacylation of Alkenes Illuminates the Mechanistic Details of the Electron Donor-Acceptor Complex-Mediated Radical Relay Processes

Progress in the development of photocatalytic reactions requires a detailed understanding of the mechanisms underpinning the observed reactivity, yet mechanistic details of many photocatalytic systems, especially those that involve electron donor-acceptor complexes, have remained elusive. We report herein the development and a combined mechanistic and computational study of photocatalytic alkene 1,2-diacylation that enables a regioselective installation of two different acyl groups, establishing direct, tricomponent access to 1,4-diketones, key intermediates in heterocyclic and medicinal chemistry. The studies revealed the central role of the electron donor-acceptor complex formed from an N-heterocyclic carbene (NHC) catalyst-derived intermediate and an acyl transfer reagent, providing a detailed description of the structural and electronic factors determining the characteristics of the photoinduced charge-transfer process that mediates photocatalytic transformation. The in-depth investigation also illuminated the roles of other radical intermediates and electron donors relevant to the catalytic activities of N-heterocyclic carbenes in radical reactions.

Oxidative acylation of α,α-diarylallylic alcohols: Synthesis of 1,2,4-triarylbutane-1,4-diones

A metal-free mediated oxidative acylation of α,α-diarylallylic alcohols with simple aromatic aldehydes for the synthesis of 1,2,4-triphenylbutane-1,4-diones is presented. In the presence of TBPB (tert-butyl peroxybenzoate), desired products were obtained in good to excellent yields for 28 examples. This protocol features high regioselectivity, wide functional group tolerance and atom economy.

Radical 1,2-Alkylarylation/Acylarylation of Allylic Alcohols with Aldehydes via Neophyl Rearrangement

A metal-free 1,2-alkylarylation of allylic alcohols with aliphatic aldehydes through concomitant radical neophyl rearrangement was developed, providing 1,2-diphenyl-3-alkyl propanones in moderate to good yields. Moreover, when cyclopropanecarbaldehyde and aryl carbaldehydes were concerned, acylarylation was involved leading to 1,4-dicarbonyl compounds.

Thiazolium-catalyzed additions of acylsilanes: A general strategy for acyl anion addition reactions

A strategy utilizing N-heterocyclic carbenes (NHCs) derived from thiazolium salts has been developed for the generation of carbonyl anions from acylsilanes. Synthetically useful 1,4-diketones and N-phosphinoyl-α- aminoketones have been prepared in good to excellent yields via NHC-catalyzed additions of acylsilanes to the corresponding α,β-unsaturated systems and N-phosphinoylimines. These organocatalytic reactions are air- and water-tolerant methods to execute robust carbonyl anion addition reactions. Additionally, polysubstituted aromatic furans and pyrroles have been efficiently synthesized in a one-pot process using this carbonyl anion methodology. The addition of alcohols to the reaction renders the process catalytic in thiazolium salt. In an effort to synthesize a potential intermediate along the proposed reaction pathway, silylated thiazolium carbinols have been identified to provide good yields of carbonyl anion addition products when subjected to the standard reaction conditions in the presence of suitable electrophiles.

The Thiazolium-Catalyzed Sila-Stetter Reaction: Conjugate Addition of Acylsilanes to Unsaturated Esters and Ketones

A new acyl anion addition reaction between acylsilanes and α,β-unsaturated conjugate acceptors promoted by a nucleophilic organic catalyst has been disclosed. The 1,4-dicarbonyl products produced in this reaction are highly useful synthons. Neutral carbenes (or zwitterions) generated in situ from commercial thiazolium salts are used as effective catalysts for the reaction which is in contrast to established anionic catalysts typically employed to promote the required Brook rearrangement (1,2-silyl shift from carbon to oxygen) involved in the reported reaction. This process successfully utilizes acylsilanes as tunable acyl anion progenitors and is tolerant of a wide range of structural diversity on the acylsilane or the conjugate acceptor. Copyright