58023-38-4

Upstream product

• 17909-51-2 (dimethyl(phenyl)silyl)(phenyl)methanone 
• 1066-35-9 dimethylmonochlorosilane 
• 59142-47-1 (2-bromophenyl)phenylmethanol 
• 100-58-3 phenylmagnesium bromide 
• 6630-33-7 ortho-bromobenzaldehyde 
• 1196117-43-7 2-(dimethyl(phenyl)silyl)-5-methoxybenzaldehyde 
• 107116-07-4 ortho-dimethylphenylsilylbenzaldehyde 
• 91-01-0 1,1-Diphenylmethanol 

Downstream Products

• 5398-11-8 3-phenylphthalide 

Relevant academic research and scientific papers

Incorporation of carbon dioxide into phthalides: Via ligand-free copper-catalyzed direct carboxylation of benzoxasiloles

The direct carboxylation of benzoxasiloles with carbon dioxide proceeded smoothly under mild conditions using copper iodide as a catalyst to afford phthalides after an acid work-up. Broad substrate scope and application of this methodology for the synthesis of natural products highlight the synthetic utility of this protocol.

SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE

Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.

Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process

A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an 2-arene:2-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.

Highly efficient activation of organosilanes with η2-aldehyde nickel complexes: Key for catalytic syntheses of aryl-, vinyl-, and alkynyl-benzoxasiloles

An η2-aldehyde nickel complex was utilized as an effective activator for an organosilane in order to generate a hypervalent silicate reactant for the first time. This method was successfully applied to the highly efficient syntheses of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles from benzaldehydes with aryl-, vinyl-, and alkynylsilyl groups at the ortho position. Initial mechanistic studies revealed that an intermolecular aryl transfer process was involved in the reaction mechanism. The formation of an η2-aldehyde complex was directly confirmed by NMR.

The design, synthesis and validation of recoverable and readily reusable siloxane transfer agents for Pd-catalyzed cross-coupling reactions

The development of competent, recoverable and reusable 1-oxa-2- silacyclopentene (siloxane) transfer agents for Pd-catalyzed cross-coupling reactions (CCRs) of organolithium reagents with aryl and alkenyl iodides has been achieved. Drawbacks of the first-generation siloxane-transfer agent (1), relating to facile recovery for potential recycling, have been addressed.

SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE

Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.