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Relevant academic research and scientific papers

Palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes

A palladium-catalyzed allylic alkylation dearomatization of β-naphthols and indoles withgem-difluorinated cyclopropanes has been developed. This reaction provided an efficient route to access 2-fluoroallylic β-naphthalenones and indolenines bearing quaternary carbon centers in good yields with highZ-selectivityviaC-C bond activation, C-F bond cleavage and the dearomatization process, benefiting from the wide substrate scope and good functional group tolerance. Moreover, 2-fluoroallylic furanoindoline and pyrroloindolines were achieved in good efficiencyviacascade allylic alkylation, dearomatization and cyclization processes in the presence of Et3B.

Rhodium Catalyzed Regioselective C?H Allylation of Simple Arenes via C?C Bond Activation of Gem-difluorinated Cyclopropanes

Herein, we report a rhodium catalyzed directing-group free regioselective C?H allylation of simple arenes. Readily available gem-difluorinated cyclopropanes can be employed as highly reactive allyl surrogates via a sequence of C?C and C?F bond activation, providing allyl arene derivatives in good yields with high regioselectivity under mild conditions. The robust methodology enables facile late-stage functionalization of complex bioactive molecules. The high efficiency of this reaction is also demonstrated by the high turnover number (TON, up to 1700) of the rhodium catalyst on gram-scale experiments. Preliminary success on kinetic resolution of this transformation is achieved, providing a promising access to enantio-enriched gem-difluorinated cyclopropanes.

Palladium-Catalyzed Defluorinative Alkylation of gem-Difluorocyclopropanes: Switching Regioselectivity via Simple Hydrazones

Conventional approaches for Pd-catalyzed ring-opening cross-couplings of gem-difluorocyclopropanes with nucleophiles predominantly deliver the β-fluoroalkene scaffolds (linear selectivity). Herein, we report a cooperative strategy that can completely switch the reaction selectivity to give the alkylated α-fluoroalkene skeletons (branched selectivity). The unique reactivity of hydrazones that enables analogous inner-sphere 3,3′-reductive elimination driven by denitrogenation, as well as the assistance of steric-embedded N-heterocyclic carbene ligand, are the key to switch the regioselectivity. A wide range of hydrazones derived from naturally abundant aryl and alkyl aldehydes are well applicable, and various gem-difluorocyclopropanes, including modified pharmaceutical and biological molecules, can be efficiently functionalized with high value alkylated α-fluorinated alkene motifs under mild conditions.

Three-component reaction ofgem-difluorinated cyclopropanes with alkenes and B2pin2for the synthesis of monofluoroalkenes

Borylative difunctionalization of alkenes has emerged as a powerful approach for synthesizing highly functionalized molecules. Herein, dual Cu/Pd-catalysed borylfluoroallylation of alkenes was smoothly achieved by usinggem-difluorinated cyclopropanes and

Visible-Light-Promoted Regioselective 1,3-Fluoroallylation of gem-Difluorocyclopropanes

A strategically novel protocol for ring-opening functionalization of aryl gem-difluorocyclopropanes (F2CPs), which allows an expedient construction of CF3-containing architectures via visible-light-promoted F-nucleophilic attack manifold, was disclosed. Single electron oxidation of F2CPs was ascribed as the critical step for the success of this transformation by prompting F-nucleophilic attack, as well as the ensuing C-C bond scission. The observed intriguing regioselectivity for fluoroincorporation in this reaction was rationalized by invoking the cation-stabilization property of gem-difluorine substituents and also the thermodynamic gains acquired from forming CF3 functionality. By using cost-effective fluorination reagent and readily available substrates, a broad collection of structurally diversified α-allyl-β-trifluoromethyl ethylbenzene derivatives could be obtained in generally good yields. Further mechanistic investigations proved the engagement of a benzylic radical intermediate in this transformation.

Ring-Opening Functionalization of Simple gem-Difluorocyclopropanes by Single-Electron Oxidants

It was reported for the first time that single-electron oxidants such as CAN or K2S2O8 affected facile ring opening of simple gem-difluorocyclopropanes to afford 1,3-dibromo-2,2-difluoropropanes in good yields by the action of KBr, and the appropriate choice of conditions allowed to incorporate not only second halogen atoms but also hydroxy or acetamido groups at the C1 position in the difluoropropane structures in a regiospecific fashion after initiation of the reaction by the introduction of the first bromine atom at the C3 position. ?

Palladium-Catalyzed Ring-Opening Coupling of gem-Difluorocyclopropanes for the Construction of 2-Fluoroallylic Sulfones

A Pd-catalyzed ring-opening sulfonylation of gem-difluorocyclopropanes is reported. This protocol involves C-C bond cleavage, β-F elimination, and allylic coupling to form corresponding 2-fluoroallylic sulfones efficiently with Z-selectivity. Different substrates bearing diverse functional groups are tolerated. Moreover, this method is successfully used for the late-stage derivation of several bioactive molecules.

Model II fluorine asia [...] inner salt synthesis and its application

The present invention provides synthesis and application of difluoro methylene phosphorus inner salt, wherein the compound has a structure shown in Formula A: (R1R2R3)P+CF2CO2 -. The definitions of substituent groups are described in the specification. Th

Difluorocarbene Addition to Alkenes and Alkynes in Continuous Flow

The first in-flow difluorocarbene generation and addition to alkenes and alkynes is reported. The application of continuous flow technology allowed for the controlled generation of difluorocarbene from TMSCF3 and a catalytic quantity of NaI. Th

Pd-Catalyzed Regioselective Activation of gem-Difluorinated Cyclopropanes: A Highly Efficient Approach to 2-Fluorinated Allylic Scaffolds

An unprecedented Pd-catalyzed regioselective activation of gem-difluorinated cyclopropanes induced by C-C bond cleavage is reported. It provides a general and efficient access to a variety of 2-fluoroallylic amines, ethers, esters, and alkylation products in high Z-selectivity, which are important skeletons in many biologically active molecules. In addition, the transformation represents the first general application of gem-difluorinated cyclopropanes as reaction partners in transition-metal-catalyzed cross-coupling reaction. C-C bond cleavage under Pd catalysis induces a regioselective activation of gem-difluorinated cyclopropanes. The reaction provides access to a variety of 2-fluoroallylic scaffolds with high Z-selectivity and represents the first general application of gem-difluorinated cyclopropanes as reaction partners in transition-metal-catalyzed cross-coupling reactions.