Synthesis of gem‐Difluorocyclopropa(e)nes and O‐, S‐, N‐, and P‐Difluoromethylated Compounds with TMSCF2Br

Li, Lingchun; Wang, Fei; Ni, Chuanfa; Hu, Jinbo

doi:10.1002/ange.201306703

Cited by 78 publications

(15 citation statements)

References 46 publications

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“…During the last decades, many new and efficient difluorocarbene sources have been developed. They were utilized in a variety of transformations including trifluoromethylations,3 difluoromethylations of alkynes4 and XH bonds (X=N, O, S),5 gem ‐difluorocyclizations,5d,f,6 gem ‐difluoroolefinations,7 and transition metal coordinations 8. With these reactions, a range of privileged functional motifs could be constructed including the difluoromethyl group which proved to be bioisosteric to amines, hydroxides and thiols with the ability to form lipophilic hydrogen bonds 9…”

Section: Methodsmentioning

confidence: 99%

The Reactivity of Difluorocarbene with Hydroxylamines: Synthesis of Carbamoyl Fluorides

et al. 2016

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Carbamoyl fluorides are formed in reactions of hydroxylamines with difluorocarbene generated from sodium bromodifluoroacetate as readily available andn on-toxic carbene precursor. The process showsahigh functional group tolerance, and the reactionp ath hasb een rationalized by computational calculations.[a] Reaction conditions:N ,N-dibenzylhydroxylamine (1a, 0.25 mmol) and BrCF 2 CO 2 Na (D,0.50 mmol) in DMF. [b] Addition of K 2 CO 3 (2 equiv.).Scheme 3. Formation of 9 from sodium bromodifluoroacetate (D)a nd N,N-dibenzylhydroxylamine( 1a)( relative free energies to D and 1a in kcal mol À1 ).

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Section: Methodsmentioning

confidence: 99%

The Reactivity of Difluorocarbene with Hydroxylamines: Synthesis of Carbamoyl Fluorides

et al. 2016

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“…150 Classical and routinely used methods to prepare difluoromethylthioethers employ appropriate thiolates and "CF 2 " species, [151][152][153] which is in most cases difluorocarbene (Scheme 28a, left). [154][155][156][157][158][159][160][161][162][163][164][165][166] These early methods suffer from a limited substrate scope and low step economy due to the harsh conditions and stepwise assembly of the -SCF 2 H moiety. In light of these issues, the Goo en group took a step forward to extend the scope by employing the Langlosis β type nucleophilic displacement of thiocyanates (-SCN) by TMSCF 2 H (Scheme 28a, right).…”

Section: Photo-induced C Sp2 -H Difluoromethylthiolation: Synthesis Omentioning

confidence: 99%

Exploration of new reaction tools for late-stage functionalization of complex chemicals

et al. 2019

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Chemistry has always had as a target the conversion of molecules into valuable materials. Nevertheless, the aim of past synthesis has primarily focused on achieving a given transformation, regardless of the environmental impact of the synthetic route. Given the current global situation, the demand for sustainable alternatives has substantially increased. Our group focuses on developing selective chemical transformations that benefit from mild conditions, improved atom economy, and that can make use of renewable feedstocks as starting materials. This account summarizes our work over the past two decades specifically regarding the selective removal, conversion, and addition of functional groups that can, later on, be applied at a late stage for the modification of complex molecules.

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“…As part of our research program towards the development of biologically active organofluorine compounds, we required reagents suitable for the difluoromethylation of C

_{sp^{3}}

‐centered nucleophiles, since they produce medicinally important difluoromethylated molecules having a quaternary carbon center. While reagents for electrophilic difluoromethylation of carbon and heteroatom nucleophiles have been reported,6, 7h,i,k,u, 8a the difluoromethylation of C

_{sp^{3}}

‐centered nucleophiles remains an area of limited success. Recently, we reported shelf‐stable reagents, S ‐(bromodifluoromethyl)diaryl sulfonium salts,7p for electrophilic difluoromethylation of C

_{sp^{3}}

‐centered nucleophiles including β‐ketoesters and dicyanoalkylidenes.…”

Section: Methodsmentioning

confidence: 99%

S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon‐Selective Electrophilic Difluoromethylation of β‐Ketoesters, β‐Diketones, and Dicyanoalkylidenes

Wang

Liu

et al. 2014

Angewandte Chemie

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S‐((Phenylsulfonyl)difluoromethyl)thiophenium salts were designed and prepared by a triflic acid catalyzed intramolecular cyclization of ortho‐ethynyl aryldifluoromethyl sulfanes. The thiophenium salts were found to be efficient as electrophilic difluoromehtylating reagents for introduction of a CF2H group to sp3‐hybridized carbon nucleophiles such as of β‐ketoesters and dicyanoalkylidenes. The (phenylsulfonyl)difluoromethyl group can be readily transformed into CF2H under mild reaction conditions. Enantioselective electrophilic difluoromethylation was also achieved in the presence of bis(cinchona) alkaloids.

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Synthesis of gem‐Difluorocyclopropa(e)nes and O‐, S‐, N‐, and P‐Difluoromethylated Compounds with TMSCF₂Br

Cited by 78 publications

References 46 publications

The Reactivity of Difluorocarbene with Hydroxylamines: Synthesis of Carbamoyl Fluorides

The Reactivity of Difluorocarbene with Hydroxylamines: Synthesis of Carbamoyl Fluorides

Exploration of new reaction tools for late-stage functionalization of complex chemicals

S‐((Phenylsulfonyl)difluoromethyl)thiophenium Salts: Carbon‐Selective Electrophilic Difluoromethylation of β‐Ketoesters, β‐Diketones, and Dicyanoalkylidenes

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