Application of alkoxy‐λ<sup>6</sup>‐sulfanenitriles as strong alkylating reagents

Wei, He; Fujii, Takayoshi; Dong, Tiaoling; Wakai, Youko; Yoshimura, Toshiaki

doi:10.1002/hc.20006

Cited by 12 publications

(5 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 1989, Yoshimura and co‐workers reported an example of an alkoxy‐λ 6 ‐sulfanenitrile 17 (Figure ). This was a powerful alkylating agent, readily converting into the corresponding sulfoximine by transfer of the R group . In 2017, Reboul described alkoxy‐λ 6 ‐sulfanenitrile 18 in the mechanistic investigation on the NH and O transfer to sulfides to form sulfoximines .…”

Section: Resultsmentioning

confidence: 99%

“…This was ap owerful alkylating agent, readily converting into the corresponding sulfoximine by transfer of the Rg roup. [28] In 2017, Reboul described alkoxy-l 6 -sulfanenitrile 18 in the mechanistic investigation on the NH and O transfer to sulfides to form sulfoximines. [17a] Compounds 5a and 5b isolated here represent an ew class of l 6 -sulfanenitriles,a nd have been fully characterized (IR, 1 Ha nd 13 CNMR, and HRMS) along with small quantities of the corresponding sulfonimidamide.T he calculated S NI R stretch (DFT) was consistent with that observed for 5b,a nd for 17.…”

Section: Angewandte Chemiementioning

confidence: 99%

See 1 more Smart Citation

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

et al. 2019

View full text Add to dashboard Cite

Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry, and provide attractive bioisosteres for sulfonamides. However, there remain few operationally simple methods for their preparation. Here, the synthesis of NH‐sulfonimidamides is achieved directly from sulfenamides, themselves readily formed in one step from amines and disulfides. A highly chemoselective and one‐pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source, and in the presence of 1 equivalent of acetic acid. A wide range of functional groups are tolerated under the developed reaction conditions, which also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel S≡N sulfanenitrile species as intermediates. Several alkoxy‐amino‐λ6‐sulfanenitriles are prepared with different alcohols, and shown to be alkylating agents to a range of nucleophiles.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Angewandte Chemiementioning

confidence: 99%

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

et al. 2019

View full text Add to dashboard Cite

show abstract

“…Bräse applied the reaction to bicyclo[1.1.1]pentyl (BCP) sulfides in the synthesis of BCP sulfoximines [ 87 ]. Zhang and Chen reported the tandem formation of sulfoximines from sulfides and intramolecular C–H amination, where (NH 4 ) 3 PO 4 ·3H 2 O was used as the ammonia source, and the reaction could be run at RT under air in methanol or in DMF [ 88 ]. With Rollin, we reported the diastereoselective preparation of glycosylsulfoximines achieving dr of up to 95:5 [ 89 ].…”

Section: Sulfides To Nh Sulfoximinesmentioning

confidence: 99%

Synthesis of Sulfoximines and Sulfonimidamides Using Hypervalent Iodine Mediated NH Transfer

Luisi

Bull

2023

Molecules

View full text Add to dashboard Cite

The development of NH transfer reactions using hypervalent iodine and simple sources of ammonia has facilitated the synthesis of sulfoximines and sulfonimidamides for applications across the chemical sciences. Perhaps most notably, the methods have been widely applied in medicinal chemistry and in the preparation of biologically active compounds, including in the large-scale preparation of an API intermediate. This review provides an overview of the development of these synthetic methods involving an intermediate iodonitrene since our initial report in 2016 on the conversion of sulfoxides into sulfoximines. This review covers the NH transfer to sulfoxides and sulfinamides, and the simultaneous NH/O transfer to sulfides and sulfenamides to form sulfoximines and sulfonimidamides, respectively. The mechanism of the reactions and the identification of key intermediates are discussed. Developments in the choice of reagents, and in the reaction conditions and setups used are described.

show abstract

Section: Angewandte Chemiementioning

confidence: 99%

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

et al. 2019

View full text Add to dashboard Cite

Sulfonimidamides are intriguing new motifs for medicinal and agrochemistry,a nd provide attractive bioisosteres for sulfonamides.However,there remain few operationally simple methods for their preparation. Here,t he synthesis of NH-sulfonimidamides is achieved directly from sulfenamides,themselves readily formed in one step from amines and disulfides.Ahighly chemoselective and one-pot NH and O transfer is developed, mediated by PhIO in iPrOH, using ammonium carbamate as the NH source,and in the presence of 1equivalent of acetic acid. Awide range of functional groups are tolerated under the developed reaction conditions,w hich also enables the functionalization of the antidepressants desipramine and fluoxetine and the preparation of an aza analogue of the drug probenecid. The reaction is shown to proceed via different and concurrent mechanistic pathways, including the formation of novel SNsulfanenitrile species as intermediates.Several alkoxy-amino-l 6 -sulfanenitriles are prepared with different alcohols,a nd shown to be alkylating agents to arange of nucleophiles. Scheme 1. Potential bioisosteres for sulfones and sulfonamides, examples of bioactive sulfonimidamides, and current strategies for the synthesis of sulfonimidamides.

show abstract

Application of alkoxy‐λ⁶‐sulfanenitriles as strong alkylating reagents

Abstract: ABSTRACT:

Cited by 12 publications

References 18 publications

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

Synthesis of Sulfoximines and Sulfonimidamides Using Hypervalent Iodine Mediated NH Transfer

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

Contact Info

Product

Resources

About

Application of alkoxy‐λ6‐sulfanenitriles as strong alkylating reagents

Abstract: ABSTRACT:

Cited by 12 publications

References 18 publications

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ6‐sulfanenitrile Intermediate

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ6‐sulfanenitrile Intermediate

Synthesis of Sulfoximines and Sulfonimidamides Using Hypervalent Iodine Mediated NH Transfer

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ6‐sulfanenitrile Intermediate

Contact Info

Product

Resources

About

Application of alkoxy‐λ⁶‐sulfanenitriles as strong alkylating reagents

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate

Synthesis of Sulfonimidamides from Sulfenamides via an Alkoxy‐amino‐λ⁶‐sulfanenitrile Intermediate