The unusual reactivity of the mono- and bis- N-(trifluoromethylsulfonyl)-substituted azaanalogs of arenesulfonochlorides

Garlyauskajte, R. Yu.; Sereda, S. V.; Yagupol’skii, L. M.

doi:10.1016/s0040-4020(01)81341-7

Cited by 33 publications

(14 citation statements)

References 5 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…PhS(NTf) 2 NH 2 ( 6 ) was synthesized based on a modified approach reported by Yagupolskii et al (see Supporting Information for further information) and has been further investigated in this work ( Scheme 5 ). 30 …”

Section: Resultsmentioning

confidence: 99%

Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity

Schwengers

Grossmann

et al. 2021

J. Am. Chem. Soc.

View full text Add to dashboard Cite

We have designed and realized an efficient and operationally simple single-flask synthesis of imidodiphosphate-based Brønsted acids. The methodology proceeds via consecutive chloride substitutions of hexachlorobisphosphazonium salts, providing rapid access to imidodiphosphates (IDP), iminoimidodiphosphates ( i IDP), and imidodiphosphorimidates (IDPi). These privileged acid catalysts feature a broad acidity range (p K a from ∼11 to <2 in MeCN) and a readily tunable confined active site. Our approach enables access to previously elusive catalyst scaffolds with particularly high structural confinement, one of which catalyzes the first highly enantioselective (>95:5 er) sulfoxidation of methyl n -propyl sulfide. Furthermore, the methodology delivers a novel, rationally designed super acidic catalyst motif, imidodiphosphorbis(iminosulfonylimino)imidate (IDPii), the extreme reactivity of which exceeds commonly employed super-Brønsted acids, such as trifluoromethanesulfonic acid. The unique reactivity of one such IDPii catalyst has been demonstrated in the first α-methylation of a silyl ketene acetal with methanol as the electrophilic alkylating reagent.

show abstract

Section: Resultsmentioning

confidence: 99%

Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity

Schwengers

Grossmann

et al. 2021

J. Am. Chem. Soc.

View full text Add to dashboard Cite

show abstract

“…The reactions are generally completed within 0.5−1.5 h. A 2-fold molar excess of 2 should be used for clean conversions. Arenesulfonyl chlorides can also be employed in this case 83a…”

Section: 17 Sulfur-based Electrophilesmentioning

confidence: 99%

Perfluoroalkylation with Organosilicon Reagents

1997

View full text Add to dashboard Cite

in the Chemistry Department at USC in the tenure track. He was promoted to full professorship in 1994. Currently, he holds the Olah Nobel Laureate Chair in Hydrocarbon Chemistry with research contributions and interests in new fluorination methods, new synthetic methods, mechanistic studies of organic reactions, electrochemistry, and superacid and hydrocarbon chemistry. He has published more than 300 papers, book chapters, and review articles; coauthored 4 books; and holds 3 patents. He has received many honors and recognition. He is currently an Advisory Editor of the International Journal of Porphyrins and Pthalocyanins.

show abstract

“…Trapping of such radical by 4‐phenylstyrene (instead of HOBt) proved impossible. Attempts to substitute N ‐tritylsulfinylamine ( 1 ) with bis(trimethylsilyl)sulfur diimide ( 4 ) in the coupling with 2 a to target a representative of the virtually unknown arylsulfondiimidates 5 or arylsulfondiimidamides 6 remained unsuccessful (Figure ). No reaction occurred, thus indicating the importance of the oxygen in reagent 1 .…”

Section: Resultsmentioning

confidence: 99%

Additions to N‐Sulfinylamines as an Approach for the Metal‐free Synthesis of Sulfonimidamides: O‐Benzotriazolyl Sulfonimidates as Activated Intermediates

et al. 2019

View full text Add to dashboard Cite

Sulfonimidamides are obtained in moderate to very good yields from the key intermediates O‐benzotriazolyl sulfonimidates, which are formed by reacting aryldiazonium tetrafluoroborates, N‐tritylsulfinylamine, and N‐hydroxybenzotriazole hydrate in a process mediated by a tertiary amine. The formation of the sulfonimidate proceeds in inexpensive and environmentally benign dimethyl carbonate as the solvent, it does not require anhydrous conditions, and the product yields generally exceed 70 %. The substrate scope is broad, and a wide range of sensitive organic functionalities is well tolerated. The reactions probably proceed via aryl radicals formed from diazonium cations with assistance from both the tertiary amine and the sulfinylamine.

show abstract

The unusual reactivity of the mono- and bis- N-(trifluoromethylsulfonyl)-substituted azaanalogs of arenesulfonochlorides

Cited by 33 publications

References 5 publications

Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity

Unified Approach to Imidodiphosphate-Type Brønsted Acids with Tunable Confinement and Acidity

Perfluoroalkylation with Organosilicon Reagents

Additions to N‐Sulfinylamines as an Approach for the Metal‐free Synthesis of Sulfonimidamides: O‐Benzotriazolyl Sulfonimidates as Activated Intermediates

Contact Info

Product

Resources

About