New chemistry of (difluoromethyl)phosphines

Burg, Anton B.

doi:10.1021/ic00215a009

Cited by 10 publications

(1 citation statement)

References 2 publications

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“…As complex 1 is a rare example of a nucleophilic reagent capable of the difluoromethylation of various electrophiles under mild reaction conditions, the development of a scalable route to this reagent is expected to increase its use in organic synthesis. Moreover, iodide 2 has found extensive use in synthesis with application in the cross-coupling with aryl Grignards, Simmons–Smith fluorocyclopropanation, Pd-catalyzed Suzuki–Miyaura and Negishi couplings, and heteroatom difluoromethylation via electrophilic alkylation . We expect the improved synthesis of intermediate 2 to also have an impact beyond the work described here.…”

Section: Introductionmentioning

confidence: 99%

Continuous Process for Preparing the Difluoromethylating Reagent [(DMPU)₂Zn(CF₂H)₂] and Improved Synthesis of the ICHF₂ Precursor

Monfette

Fang

Bio

et al. 2020

Org. Process Res. Dev.

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Complex [(DMPU) 2 Zn(CF 2 H) 2 ] 1 is a crystalline organometallic reagent with utility in various catalytic difluoromethylation reactions under mild conditions. Unfortunately, this reagent is not commercially available and the procedure for the preparation of this air-and moisture-sensitive zinc complex has only been reported on a small scale. Herein, we report the development of a continuous process for the preparation of reagent 1 on >100 g scale by using a continuous stirred-tank reactor. The key to success is the design of a continuous reactive crystallization process in which the precipitation of the zinc complex 1 is driven by its low solubility in the reaction solvent. The improved synthesis of the iododifluoromethane precursor 2 from readily available bromodifluoroacetic acid further enables the synthesis of complex 1 on a larger scale.

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