Reaction of Thiocarbonyl Fluoride Generated from Difluorocarbene with Amines

Yu, Jiao; Lin, Jin‐Hong; Xiao, Ji‐Chang

doi:10.1002/ange.201710186

Cited by 18 publications

(10 citation statements)

References 79 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Chlorodifluoromethane (ClCF 2 H) is well known as an inexpensive and abundant industrial raw material (Hudlicky and Pavlath, 1995) for the construction of various fluorinated compounds (Wang et al., 2014, Fier and Hartwig, 2012, Gu et al., 2014, Yu et al., 2017, Wu et al., 2019, Miao et al., 2018, Zhang et al., 2019), featuring thermodynamic stability and kinetic inertness as well as atomic economy as fluorine source. Therefore, efficient transformations of this easily accessible raw material to create valuable chemicals have deservedly gained great attention.…”

Section: Introductionmentioning

confidence: 99%

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Zhang

et al. 2019

iScience

View full text Add to dashboard Cite

Summary The development of C1 synthons to afford the products that add one extra carbon has become an important research theme in the past decade, and significant progress has been achieved with CO 2 , CO, HCOOH, and others as C1 units. Despite the great advance, the search for new C1 synthons that display unique reactivity, complement to the current C1 sources, and add more value to C1 chemistry is still desirable. Herein, we report a quadruple cleavage of chlorodifluoromethane to yield a C1 source, which was successfully employed in the construction of various N -containing compounds especially with pharmaceutical molecules under mild conditions. This strategy provides a useful method for late-stage modification of pharmaceutical compounds. Four bonds in ClCF 2 H were orderly cleaved under basic conditions in the absence of transition metals. Preliminary mechanistic studies revealed that ( E )- N -phenylformimidoyl fluoride intermediate is involved in this process by in situ 1 H NMR studies and control experiments.

show abstract

Section: Introductionmentioning

confidence: 99%

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Zhang

et al. 2019

iScience

View full text Add to dashboard Cite

show abstract

“…In contrast to perfluoroalkyl and perfluoroalkoxy groups, the chemistry of related perfluoroalkyl nitrogen substituents has been studied to a much lesser extent. Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years [28–38] . Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials [18,39–40] .…”

Section: Figurementioning

confidence: 99%

“…Some synthetic strategies towards N ‐trifluoromethylamines and related N ‐perfluoroalkylnitrogen derivates have been developed in recent years. [ 28 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 ] Efficient strategies towards N , N ‐bis(perfluoroalkyl)nitrogen compounds remain scarce, presumably, because of the lack of suitable starting materials. [ 18 , 39 , 40 ] Especially the N , N ‐bis(trifluoromethyl)amino group is of interest as its organic derivatives are known to exhibit high stability, for example against acids and bases,[ 1 , 41 ] and because its potential as substituent in pharmaceuticals was demonstrated, earlier.…”

mentioning

confidence: 99%

Stable and Storable N(CF₃)₂ Transfer Reagents

Schneider

Krauel

Deutsch

et al. 2021

Chemistry A European J

View full text Add to dashboard Cite

Fluorinated groups are essential for drug design, agrochemicals, and materials science. The bis(trifluoromethyl) amino group is an example of a stable group that has a high potential. While the number of molecules containing perfluoroalkyl, perfluoroalkoxy, and other fluorinated groups is steadily increasing, examples with the N(CF 3 ) 2 group are rare. One reason is that transfer reagents are scarce and metalbased storable reagents are unknown. Herein, a set of Cu I and Ag I bis(trifluoromethyl)amido complexes stabilized by N-and P-donor ligands with unprecedented stability are presented. The complexes are stable solids that can even be manipulated in air for a short time. They are bis(trifluoromethyl) amination reagents as shown by nucleophilic substitution and Sandmeyer reactions. In addition to a series of benzylbis (trifluoromethyl)amines, 2-bis(trifluoromethyl)amino acetate was obtained, which, upon hydrolysis, gives the fluorinated amino acid N,N-bis(trifluoromethyl)glycine.Transition metal perfluoroalkyl complexes are highly valuable reagents for the synthesis of fluorinated biologically active molecules that are employed as pharmaceuticals or agrochemicals and in materials applications. [1][2][3][4][5][6] Especially, copper(I) complexes are important as they enable the introduction of a broad variety of perfluoroalkyl groups into organic molecules that range from the simplest congener, trifluoromethyl, to longer linear and branched perfluoroalkyl groups such as the heptafluoroisopropyl (hfip) group. [7][8][9][10] Although many of these complexes are used either in situ or immediately after generation, some complexes have been isolated and characterized, in detail. These complexes are often stabilized by co-ligands that typically are pyridines or phosphanes, for example [(bpy)CuC 2 F 5 ] (Figure 1) [11] and [(Ph 3 P) 2 Cu{CF(CF 3 ) 2 }] ([(Ph 3 P) 2 Cu(hfip)]). [12] Silver (I) complexes have been employed as perfluoroalkylation reagents as well, [13][14] although to a lesser extent than the related copper(I) derivatives. Because of their easy accessibility using silver(I) fluoride and the respective perfluoroalkene, for example, heptafluoropropene and tetrafluoroethylene, [15] they[a] L.

show abstract

“…In recent years, several new methods have been developed for the synthesis of ITCs, using fluorine-containing reagents such as Langlois reagent (F 3 CSO 2 Na) [ 39 ], Ph 3 P + CF 3 CO 2 − (PDFA)/S 8 [ 40 ], (Me 4 N)SCF 3 [ 41 ], CF 3 SiMe 3 /S 8 or AgSCF 3 [ 42 ], and BrCF 2 CO 2 Na/S 8 [ 43 ]. However, three methods still predominate.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Isothiocyanates Using DMT/NMM/TsO− as a New Desulfurization Reagent

2021

View full text Add to dashboard Cite

Thirty-three alkyl and aryl isothiocyanates, as well as isothiocyanate derivatives from esters of coded amino acids and from esters of unnatural amino acids (6-aminocaproic, 4-(aminomethyl)benzoic, and tranexamic acids), were synthesized with satisfactory or very good yields (25–97%). Synthesis was performed in a “one-pot”, two-step procedure, in the presence of organic base (Et3N, DBU or NMM), and carbon disulfide via dithiocarbamates, with 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium toluene-4-sulfonate (DMT/NMM/TsO−) as a desulfurization reagent. For the synthesis of aliphatic and aromatic isothiocyanates, reactions were carried out in a microwave reactor, and selected alkyl isothiocyanates were also synthesized in aqueous medium with high yields (72–96%). Isothiocyanate derivatives of L- and D-amino acid methyl esters were synthesized, under conditions without microwave radiation assistance, with low racemization (er 99 > 1), and their absolute configuration was confirmed by circular dichroism. Isothiocyanate derivatives of natural and unnatural amino acids were evaluated for antibacterial activity on E. coli and S. aureus bacterial strains, where the most active was ITC 9e.

show abstract

Reaction of Thiocarbonyl Fluoride Generated from Difluorocarbene with Amines

Cited by 18 publications

References 79 publications

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Stable and Storable N(CF₃)₂ Transfer Reagents

Synthesis of Isothiocyanates Using DMT/NMM/TsO− as a New Desulfurization Reagent

Contact Info

Product

Resources

About

Reaction of Thiocarbonyl Fluoride Generated from Difluorocarbene with Amines

Cited by 18 publications

References 79 publications

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Chlorodifluoromethane as a C1 Synthon in the Assembly of N-Containing Compounds

Stable and Storable N(CF3)2 Transfer Reagents

Synthesis of Isothiocyanates Using DMT/NMM/TsO− as a New Desulfurization Reagent

Contact Info

Product

Resources

About

Stable and Storable N(CF₃)₂ Transfer Reagents