Thionyl Fluoride-Mediated One-Pot Substitutions and Reductions of Carboxylic Acids

Bolduc, Trevor G; Lee, Cayo; Chappell, William P; Sammis, Glenn M.

doi:10.1021/acs.joc.2c00496

Cited by 15 publications

(8 citation statements)

References 96 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We next considered the mechanism of this unique amidation reaction. 9,10,17 During the initial step, the anion of carboxylic acid I, formed in the presence of the base NMM, reacts with the electrophilic sulfonyl center of II leading to the formation of carboxylic sulfurofluoridic anhydride intermediate III. Subsequent nucleophilic substitution with the amine, deprotonation and elimination of OSO 2 F leads to the generation of the desired amide product VI (Scheme 5).…”

Section: Scheme 4 a Gram-scale Reactionmentioning

confidence: 99%

Synthesis of Amides and Peptides by Employing [4-(Acetylamino) phenyl]imidodisulfuryl Difluoride (AISF) as a Coupling Reagent

Bharamawadeyar,

Chetankumar,

Srinivasulu

et al. 2024

Synthesis

View full text Add to dashboard Cite

A new synthetic approach for the preparation of amides and peptides containing amino acids as well as aryl acids and amines by employing [4-(acetylamino)phenyl]imidodisulfuryl difluoride (AISF) as a carboxylic acid activator under mild conditions is delineated. The use of AISF as an acid activator allows the reaction to be performed efficiently. This operationally simple amidation is amenable to a wide variety of carboxylic acids and Nα-protected amino acids. Further, racemization did not occur during the coupling. In addition, a gram-scale reaction is demonstrated.

show abstract

Section: Scheme 4 a Gram-scale Reactionmentioning

confidence: 99%

Synthesis of Amides and Peptides by Employing [4-(Acetylamino) phenyl]imidodisulfuryl Difluoride (AISF) as a Coupling Reagent

Bharamawadeyar,

Chetankumar,

Srinivasulu

et al. 2024

Synthesis

View full text Add to dashboard Cite

show abstract

“…Next, we conducted a comparative analysis of our ball milling system with the reported batch reactions for the synthesis of dipeptides 4vj and 4wj (Table 2), as described by Sammis et al 60 and Maruoka et al 76 (entries 1 and 2). Notably, both batch reactions rely on the use of solvents, such as DCM and acetonitrile (MeCN), whereas our mechanochemical method operates without any solvent.…”

Section: Acs Sustainablementioning

confidence: 99%

Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation

Zhao,

Ikawa,

Mori

et al. 2024

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

Diverse methods have been reported for the synthesis of acyl fluorides; however, an environmentally benign synthesis method for acyl fluorides remains underdeveloped. In this study, we developed solvent-free mechanochemical deoxyfluorination of carboxylic acids to acyl fluorides mediated by 1,1,2,2-tetrafluoroethyl-N,N-dimethylamine (TFEDMA) using a ball mill. This method facilitated high product yields in short reaction times even for sterically challenged carboxylic acids. We also realized the mechanochemical coupling of acyl fluorides and amines as well as the TFEDMA-mediated direct mechanochemical coupling reaction of carboxylic acids with amines via a sequential one-pot deoxyfluorination/coupling pathway. Furthermore, this protocol was expanded to include peptide synthesis. The efficiency of the protocol, in terms of speed, solvent-free characteristics, and favorable E-factor, aligns well with the requirements of current environmental policies.

show abstract

“…Its aptitude in aliphatic and aromatic acyl fluorides, amino acid couplings, and peptide synthesis has been demonstrated. These new chemistries appear to open broad scope for a wide range of applications of SOF 2 for rational organic synthesis, for instance, the SOF 2 ‐mediated one‐pot substitutions and reductions of carboxylic acids [28].…”

Section: Introductionmentioning

confidence: 99%

Computational study of the atmospheric oxidation and global warming potential of thionyl fluoride

Gao

Hou

Zhang

et al. 2023

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Thionyl fluoride (SOF2) is the dominant decomposition by‐product in SF6 under electrical discharges and a novel fluorinating reagent for organic synthesis to replace sulfuryl fluoride (SO2F2). Since both SF6 and SO2F2 are strong green‐house gases, for the sake of environmental concern, tropospheric oxidation of SOF2 by OH radicals in the presence of O2 has been investigated using various computational methods including density functional M06‐2X, coupled‐cluster (CCSD), the explicitly correlated RCCSD(T)‐F12, Gaussian‐4, ROCBS‐QB3, and Weizmann‐1 theories. The SO bond association between SOF2 and OH proceeds via the barriers of 1–3 kcal/mol to form various shallow wells HOSOF2 (−3 to −8 kcal/mol) linked by Berry pseudorotations and followed by HF‐elimination. Interception of the HOSOF2 adducts by O2 produce HO2 and SO2F2 predominantly via the concerted SO bond association/dissociation and proton‐transfer. The atmospheric lifetime and radiative efficiency for SOF2 were calculated to be 1.2–1.5 years and 0.223 W/m2/ppb, respectively. The global warming potential of SOF2 was estimated to be 169–211, as indicative of an eco‐friendly gas. However, the environmental impact of SOF2 should take into account the production of SO2F2 and HO2 due to oxidation.

show abstract

Thionyl Fluoride-Mediated One-Pot Substitutions and Reductions of Carboxylic Acids

Cited by 15 publications

References 96 publications

Synthesis of Amides and Peptides by Employing [4-(Acetylamino) phenyl]imidodisulfuryl Difluoride (AISF) as a Coupling Reagent

Synthesis of Amides and Peptides by Employing [4-(Acetylamino) phenyl]imidodisulfuryl Difluoride (AISF) as a Coupling Reagent

Mechanochemical Deoxyfluorination of Carboxylic Acids to Acyl Fluorides and Successive Mechanochemical Amide Bond Formation

Computational study of the atmospheric oxidation and global warming potential of thionyl fluoride

Contact Info

Product

Resources

About