Sulfonyl fluorides as targets and substrates in the development of new synthetic methods

Nature Reviews Chemistry, Год журнала: 2022, Номер 6(2), С. 146 - 162

Опубликована: Янв. 19, 2022

Язык: Английский

---

EnT-Mediated N–S Bond Homolysis of a Bifunctional Reagent Leading to Aliphatic Sulfonyl Fluorides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2364 - 2374

Опубликована: Янв. 18, 2023

Sulfur(VI) fluoride exchange (SuFEx) gives rise to a plethora of high-valent sulfur linkages; however, the availability (aliphatic) sulfonyl manifolds lag behind, owing limited sources introducing SO2F moiety via classical two-electron approach. Recently, radical-based methodologies have emerged as complementary strategy increase diversity accessible click partners. In this work, synthesis bench-stable sulfamoyl reagent is presented, which may undergo sigma-bond homolysis upon visible-light-induced sensitization form protected β-amino fluorides from alkene feedstocks. Notably, offers an appealing access various building blocks for peptido fluorides, relevant in medicinal chemistry context, well intriguing entry β-ammonium sulfonates and β-sultams, alkenes. Densely functionalized 1,3-sultones were obtained by employing allyl alcohols substrates. Surprisingly, chloride-derived β-imino underwent S-O bond formation ring closure yield rigid cyclopropyl sulfonate ester under SuFEx conditions. Furthermore, engaging thiol-based hydrogen atom donor reaction, reactivity same can be tuned toward direct aliphatic fluorides. Mechanistic experiments indicate energy transfer (EnT)-mediated process. The transient radical adds product occurs either radical-radical coupling or (HAT), respectively.

Язык: Английский

---

Sulfur fluoride exchange

Nature Reviews Methods Primers, Год журнала: 2023, Номер 3(1)

Опубликована: Авг. 3, 2023

Язык: Английский

---

Emerging Building Blocks for Medicinal Chemistry: Recent Synthetic Advances

European Journal of Organic Chemistry, Год журнала: 2021, Номер 2021(47), С. 6478 - 6510

Опубликована: Сен. 8, 2021

Abstract Current medicinal chemistry relies heavily on the quality of building blocks, i. e. reagents used to introduce chemical diversity into target molecules. The last decade witnessed an emergence many novel (or well‐overlooked old) chemotypes for drug discovery, which is related adapting new synthetic methodologies, designing sp 3 ‐enriched bioisosteres, paying attention previously underrated even unwanted) structural motifs, or combination thereof. In this review with 532 references, a survey selected that emerged recently in provided, focus synthesis corresponding blocks. Thus, saturated (hetero)aliphatic boronates, sulfonyl fluorides, sulfinates, non‐classical benzene isosteres, bicyclic morpholine/piperidine/piperazine analogs, as well gem ‐difluorinated cycloalkanes (as example emerging fluorinated motifs) are discussed.

Язык: Английский

---

Accelerated SuFEx Click Chemistry For Modular Synthesis**

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(4)

Опубликована: Ноя. 10, 2021

Abstract SuFEx click chemistry is a powerful method designed for the selective, rapid, and modular synthesis of functional molecules. Classical reactions form stable S−O linkages upon exchange S−F bonds with aryl silyl‐ether substrates, while near‐perfect in their outcome, are sometimes disadvantaged by relatively high catalyst loadings prolonged reaction times. We herein report development accelerated (ASCC), an improved efficient catalytic coupling alkyl alcohols range SuFExable hubs. demonstrate Barton's hindered guanidine base (2‐tert‐butyl‐1,1,3,3‐tetramethylguanidine; BTMG) as superb that, when used synergy silicon additive hexamethyldisilazane (HMDS), yields bond single step; often within minutes. The combination BTMG HMDS reagents allows low 1.0 mol % and, congruence click‐principles, provides scalable that safe, efficient, practical synthesis. ASSC expands number accessible products will find significant application organic synthesis, medicinal chemistry, chemical biology, materials science.

Язык: Английский

---

Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(51), С. 21497 - 21502

Опубликована: Дек. 16, 2021

A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within catalytic cycle without modifying oxidation state. All have been validated, including insertion SO2 into Bi-C bonds, leading to structurally unique O-bound bismuth sulfinate complex. The protocol affords excellent yields for wide range aryl and heteroaryl acids, displaying functional group tolerance.

Язык: Английский

---

Photoredox catalytic radical fluorosulfonylation of olefins enabled by a bench-stable redox-active fluorosulfonyl radical precursor

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Июнь 11, 2022

Abstract Sulfonyl fluorides have attracted considerable and growing research interests from various disciplines, which raises a high demand for novel effective methods to access this class of compounds. Radical flurosulfonylation is recently emerging as promising approach the synthesis sulfonyl fluorides. However, scope applicable substrate reaction types are severely restricted by limited known radical reagents. Here, we introduce solid state, redox-active type fluorosulfonyl reagents, 1-fluorosulfonyl 2-aryl benzoimidazolium triflate (FABI) salts, enable fluorosulfonylation olefins under photoredox conditions. In comparison with precursor, gaseous FSO 2 Cl, FABI salts bench-stable, easy handle, affording yields in before challenging substrates. The advantage FABIs further demonstrated development an alkoxyl-fluorosulfonyl difunctionalization olefins, forges facile useful β-alkoxyl related compounds, would thus benefit study context chemical biology drug discovery future.

Язык: Английский

---

Divergent sulfur(VI) fluoride exchange linkage of sulfonimidoyl fluorides and alkynes

Nature Synthesis, Год журнала: 2022, Номер 1(6), С. 455 - 463

Опубликована: Май 9, 2022

Язык: Английский

---

(Hetero)aryl‐S^VI Fluorides: Synthetic Development and Opportunities

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(23)

Опубликована: Март 18, 2022

(Hetero)arylsulfur compounds where the S atom is in oxidation state VI represent a large percentage of molecular functionalities present organic chemistry. More specifically, (hetero)aryl-S

Язык: Английский

---

Amino-oxetanes as amide isosteres by an alternative defluorosulfonylative coupling of sulfonyl fluorides

Nature Chemistry, Год журнала: 2022, Номер 14(2), С. 160 - 169

Опубликована: Янв. 27, 2022

Язык: Английский

---