Arylsulfonyl fluoride boronic acids: Preparation and coupling reactivity

Lou, Terry Shing‐Bong; Willis, Michael C.

doi:10.1016/j.tet.2019.130782

Cited by 19 publications

(24 citation statements)

References 36 publications

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“…[1][2][3] The SO 2 F group is often installed through transition-metal catalyzed processes, [6][7][8][9][10][11][12][13][14][15][16][17][18] and has been reported to be inert under Suzuki-Miyaura coupling (SMC) conditions. [3,[19][20][21] As a result, while sulfonyl fluorides are a powerful tool to access sulfonylated derivatives, their use as SMC electrophiles to form C À C bonds would significantly broaden their synthetic utility. However, despite the importance of the SO 2 F group and substantial efforts to widen the scope of the SMC reaction to include sulfones and sulfonyl chlorides, [22][23][24][25][26][27][28][29][30][31] a method for CÀC cross-coupling of sulfonyl fluorides has yet to be developed (Scheme 1 B).…”

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confidence: 99%

“…Other functional groups on the boronic acid were also found to be tolerated, including vinyl substitution (5), aromatic amines (6), benzyl ethers (8,17,24), aldehydes (10), and dioxy methylene groups (14). Pyridyl sulfonyl fluorides substituted with electron-donating or electron-withdrawing groups displayed good reactivity using Cu(IPr)Cl and KHF 2 as additives (12)(13)(14)(15)(16)(17)(18)(19)(20)(21). Substitution ortho to the sulfonyl fluoride leaving group was tolerated (19).…”

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confidence: 99%

“…Pyridyl sulfonyl fluorides substituted with electron-donating or electron-withdrawing groups displayed good reactivity using Cu(IPr)Cl and KHF 2 as additives (12)(13)(14)(15)(16)(17)(18)(19)(20)(21). Substitution ortho to the sulfonyl fluoride leaving group was tolerated (19). Unsuccessful attempts to couple other heterocyclic sulfonyl fluorides are documented in Table S5.…”

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confidence: 99%

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Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Chatelain

Muller

et al. 2021

Angew Chem Int Ed

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Sulfonyl fluorides have emerged as powerful "click" electrophiles to access sulfonylated derivatives. Yet, they are relatively inert towards C À C bond forming transformations, notably under transition-metal catalysis. Here, we describe conditions under which aryl sulfonyl fluorides act as electrophiles for the Pd-catalyzed Suzuki-Miyaura cross-coupling. This desulfonative cross-coupling occurs selectively in the absence of base and, unusually, even in the presence of strong acids. Divergent one-step syntheses of two analogues of bioactive compounds showcase the expanded reactivity of sulfonyl fluorides to encompass both SÀNu and CÀC bond formation. Mechanistic experiments and DFT calculations suggest oxidative addition occurs at the CÀS bond followed by desulfonation to form a Pd-F intermediate that facilitates transmetalation.

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Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Chatelain

Muller

et al. 2021

Angew Chem Int Ed

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“…The introduction of both chloride and the fluorosulfonyl group at the same time onto the triple bond affords the chance to develop modular synthetic methods based on BCASF hubs by further manipulations on these functional groups. We first examined the compatibility and reactivity of BCASF hubs in the Suzuki coupling [12b,f,i, 16] of 3 a with phenylboronic acid (Scheme 1 A). To our delight, after a careful optimization of the reaction conditions, a high yield can be finally achieved by performing the reactions in MeCN at 110 °C.…”

Section: Resultsmentioning

confidence: 99%

Introducing A New Class of Sulfonyl Fluoride Hubs via Radical Chloro‐Fluorosulfonylation of Alkynes

Nie

Hong

et al. 2021

Angewandte Chemie

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Sulfonyl fluorides have widespread applications in many important fields, including ligation chemistry, chemical biology, and drug discovery. Therefore, new methods to increase the synthetic efficiency and expand the available structures of sulfonyl fluorides are highly in demand. Here, we introduce a new and powerful class of sulfonyl fluoride hubs, β‐chloro alkenylsulfonyl fluorides (BCASF), which can be constructed via radical chloro‐fluorosulfonyl difunctionalization of alkynes under photoredox conditions. BCASF molecules exhibit versatile reactivities and well undergo a series of transformations at the chloride site while keeping the sulfonyl fluoride group intact, including reduction, Suzuki coupling, Sonogashira coupling, as well as nucleophilic substitution with various nitrogen, oxygen, and sulfur nucleophiles. By using BCASF as a synthetic hub, a wide range of sulfonyl fluorides becomes readily accessible, such as cis alkenylsulfonyl fluorides, dienylsulfonyl fluorides, and ynenylsulfonyl fluorides, which are challenging or even not possible to synthesize before with the known methods. Moreover, further application of BCASF to the late‐stage modification of peptides and drugs is also demonstrated.

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“…To further demonstrate the compatibility of this chemistry with transition metal‐mediated processes, the boronate ester containing substrate 12 was prepared using an Ir‐catalyzed borylation reaction (Scheme 4 b). [28] The bifunctional pyridine 12 underwent SMC with 4‐bromotoluene 2 b to give sulfone 13 in 62 % yield; [29] notably, the masked sulfinate functionality remained intact. Finally, diarylpyridine 14 was obtained in excellent 92 % yield from biaryl sulfone 13 using our standard cross‐coupling protocol.…”

Section: Resultsmentioning

confidence: 99%

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

et al. 2021

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Heteroaromatic sulfinates are effective nucleophilic reagents in Pd0‐catalyzed cross‐coupling reactions with aryl halides. However, metal sulfinate salts can be challenging to purify, solubilize in reaction media, and are not tolerant to multi‐step transformations. Here we introduce base‐activated, latent sulfinate reagents: β‐nitrile and β‐ester sulfones. We show that under the cross‐coupling conditions, these species generate the sulfinate salt in situ, which then undergo efficient palladium‐catalyzed desulfinative cross‐coupling with (hetero)aryl bromides to deliver a broad range of biaryls. These latent sulfinate reagents have proven to be stable through multi‐step substrate elaboration, and amenable to scale‐up.

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Arylsulfonyl fluoride boronic acids: Preparation and coupling reactivity

Cited by 19 publications

References 36 publications

Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Desulfonative Suzuki–Miyaura Coupling of Sulfonyl Fluorides

Introducing A New Class of Sulfonyl Fluoride Hubs via Radical Chloro‐Fluorosulfonylation of Alkynes

Base‐Activated Latent Heteroaromatic Sulfinates as Nucleophilic Coupling Partners in Palladium‐Catalyzed Cross‐Coupling Reactions

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