S<sup>VI</sup>–C Linkage for Allylsulfonximines via BF<sub>3</sub>-Mediated Allylation

Zeng, Daming; Zhao, Shiyong; Deng, Wei‐Ping; Jiang, Xuefeng

doi:10.1021/acs.orglett.3c01902

Org. Lett.

2023

DOI: 10.1021/acs.orglett.3c01902

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S^VI–C Linkage for Allylsulfonximines via BF₃-Mediated Allylation

Daming Zeng

Shiyong Zhao

Wei‐Ping Deng

et al.

Abstract: A SuFEx linkage reaction between sulfonimidoyl fluoride and allyltrimethylsilane was achieved for the construction of N-modified allylsulfoximines in minutes with BF3 as a nonmetal difunctional activator enabling the activation of both S–F and C–Si bonds to forge the S–Callyl (sp3) bond swiftly. Mechanistic studies and DFT calculations indicated that the linkage was initiated with the activation of sulfonimidoyl fluoride and then followed with the transfer of the fluoride anion to the TMS group.

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2024

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Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Gais

2024

Eur J Org Chem

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The combination of a sulfonimidoyl and aminosulfoxonium group with a double bond renders vinyl sulfoximines and vinyl aminosulfoxonium salts particularly versatile classes of compounds in organic synthesis. The discussion of vinyl sulfoximines includes in addition to the synthesis, the Michael reaction and its application in stereoselective synthesis, the synthesis, structure and application of a‐lithiovinyl sulfoximines, the nickel‐catalyzed and copper‐mediated anionic cross‐coupling reaction of a‐metallovinyl sulfoximines, the synthesis of acyclic and cyclic dienyl vinyl sulfoximines and the ring‐closing metathesis, the hydroalumination and reductive Pauson‐Khand reaction, the nickel‐catalyzed cross‐coupling reaction, the vinyl‐allyl isomerization, and the cycloaddition. The discussion of vinyl aminosulfoxonium salts includes in addition to the synthesis, the Michael reaction, the ethylenation of protic nucleophiles, the synthesis of allyl aminosulfoxonium salts and the nucleophilic substitution, the synthesis of allyl aminosulfoxonium ylides and the imino ester aziridination, the synthesis of vinyl aminosulfoxonium ylides, the synthesis of alkynes and dihydrofurans, the nickel‐catalyzed cross‐coupling reaction, and the intramolecular substitution of the amino group.

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Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Gais

2024

Eur J Org Chem

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Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

Zou,

Sun,

Hong

et al. 2024

J. Phys. Chem. A

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This study elucidates the mechanisms and principles governing chemoselectivity in synthesizing two distinct Nheterocycles, benzimidazole thiazine and benzothiazole imidazole, through BF 3 •OEt 2 -catalyzed cyclization reactions of propargyl alcohols with benzimidazole thiols. Employing density functional theory calculations, we highlight the crucial role of fluorine source in influencing chemoselectivity. In DCM, BF 3 , as the catalytic center, coordinates with propargyl alcohol's hydroxyl group to form a precursor. Conversely, in DMF, [BF 2 •DMF] + , formed from DMF and BF 3 •OEt 2 , acts as the catalytic center, activating the propargyl alcohol's hydroxyl group. The mechanisms in both solvents involve sequential steps: B−O bond formation, C−O bond cleavage, S− C bond formation, hydrogen atom transfer (HAT), cyclization, and deprotonation. A notable difference is the HAT process: in DCM, it follows a 1,5-HAT process, while in DMF, BF 4 − formation from DMF and BF 3 •OEt 2 provides a fluorine source and introduces steric hindrance, favoring a 1,6-HAT process and leading to unique chemoselectivity. This pioneering research showcases the impact of DMF on cyclization reactions, offering valuable insights for comprehending and designing reactions driven by fluorine sources. Crucially, our results propose an innovative reaction mechanism featuring lower potential energy surfaces, enhancing our understanding of the intricate interplay among reactants, catalysts, and solvents.

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C-SuFEx linkage of sulfonimidoyl fluorides and organotrifluoroborates

Zhao,

Zeng,

Wang

et al. 2024

Nat Commun

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Sulfur(VI) fluoride exchange, a new type of linkage reaction, has excellent potential for application in functional molecule linkage to prepare pharmaceuticals, biomolecules, and polymers. Herein, a C-SuFEx reaction is established to achieve fast (in minutes) linkage between sulfonimidoyl fluorides and aryl/alkyl organotrifluoroborates. Potassium organotrifluoroborates are instantaneously activated via a substoichiometric amount of trimethylsilyl triflate to afford organodifluoroboranes, releasing BF3 as an activating reagent in situ. This sulfur(VI) fluoride exchange technique is capable of forming S(VI)-C(alkyl), S(VI)-C(alkenyl) and S(VI)-C(aryl) bonds, demonstrating its broad scope. Natural products and pharmaceuticals with sensitive functional groups, such as valdecoxib, celecoxib and diacetonefructose, are compatible with this protocol, allowing the formation of diverse sulfoximines.

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S^VI–C Linkage for Allylsulfonximines via BF₃-Mediated Allylation

Cited by 3 publications

References 46 publications

Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

C-SuFEx linkage of sulfonimidoyl fluorides and organotrifluoroborates

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SVI–C Linkage for Allylsulfonximines via BF3-Mediated Allylation

Cited by 3 publications

References 46 publications

Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Synthesis, Reactivity and Application of Vinyl Sulfoximines and Vinyl Aminosulfoxonium Salts

Theoretical Insights into the Mechanism and Origin of Solvent-Dependent Selectivity in the Cyclization of Propargyl Alcohols for the Divergent Synthesis of N-Heterocycles

C-SuFEx linkage of sulfonimidoyl fluorides and organotrifluoroborates

Contact Info

Product

Resources

About

S^VI–C Linkage for Allylsulfonximines via BF₃-Mediated Allylation