A Synthesis of “Dual Warhead” β-Aryl Ethenesulfonyl Fluorides and One-Pot Reaction to β-Sultams

Samipillai

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2017

Self Cite

Section: Discussionmentioning

confidence: 99%

Crystal structure of methyl 1-(2-(fluorosulfonyl)ethyl)-2-oxocyclopentanecarboxylate, C₉H₁₃FO₅S

Samipillai

Zeitschrift Für Kristallographie - New Crystal Structures

et al. 2017

Self Cite

“…In 2017, Arvidsson and co-workers reported an operationally simple method for ligand-and additive-free oxidative Heck couplings of aryl boronic acids (57) with ESF (51) (Scheme 10) [65]. The reactions proceeded at room temperature with good chemoselectivity and E-selectivity and offered facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides (58) from the commercially available boronic acids (57).…”

Section: Fluorine-containing Vinyl Sulfur Compounds As the Cross-coupmentioning

confidence: 99%

“…Furthermore, the oxidative Heck cross-coupling reactions have become attractive for modern organic synthesis due to advantages such as efficiency, mild reaction conditions, good functional group tolerance, and widespread applications [62][63][64]. In 2017, Arvidsson and co-workers reported an operationally simple method for ligand-and additive-free oxidative Heck couplings of aryl boronic acids (57) with ESF (51) (Scheme 10) [65]. The reactions proceeded at room temperature with good chemoselectivity and E-selectivity and offered facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides (58) from the commercially available boronic acids (57).…”

Section: Fluorine-containing Vinyl Sulfur Compounds As the Cross-coupmentioning

confidence: 99%

“…The reactions proceeded at room temperature with good chemoselectivity and E-selectivity and offered facile access to a wide range of β-aryl/heteroaryl ethenesulfonyl fluorides (58) from the commercially available boronic acids (57). The products (58) have a "dual warhead" with two electrophilic sites that have been used as covalent enzyme inhibitors and as synthetic reagents [65]. The authors also demonstrated that aryl-substituted β-sultams could be prepared through a one-pot procedure in which an excess of primary amine was added to the reaction mixture before workup [65].…”

Section: Fluorine-containing Vinyl Sulfur Compounds As the Cross-coupmentioning

confidence: 99%

See 1 more Smart Citation

Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners

Yang

Zhao

et al. 2018

Catalysts

Abstract:The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes. Variants of the Pd-catalyzed Mizoroki-Heck reactions with fluorine-containing reagents are also briefly depicted. This work supplies an overview, as well as a guide, to both younger and more established researchers in order to attract more attention and contributions in the realm of Mizoroki-Heck reactions with fluorine-containing participants.

“…Figure 1b(2)]. [14] In pursuit of a more general Heck-type coupling process with ESF, [15], [16] we turned to organic iodides. Although the preliminary attempts using phosphine ligand or base failed (see SI), the combination of aryl halide/silver(I) salt [17] was found the fix for this palladium catalyzed coupling process between iodobenzene (2a) and ESF (1) (equation 1).…”

Section: Hhs Public Accessmentioning

confidence: 99%

Palladium‐Catalyzed Fluorosulfonylvinylation of Organic Iodides

et al. 2017

A palladium-catalyzed fluorosulfonylvinylation reaction of organic iodides is described. Catalytic Pd(OAc) 2 with stoichiometric silver(I) trifluoroacetate enables the coupling process between an (hetero)aryl or alkenyl iodide and ethenesulfonyl fluoride (ESF, 1). The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds in up to 99% yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides, and 1,3-dienylsulfonyl fluorides. FluorosulfonylvinylationCatalytic Pd(OAc) 2 with stoichiometric silver(I) trifluoroacetate enables the coupling process between an (hetero)aryl or alkenyl iodide and ethenesulfonyl fluoride. The method is demonstrated in the successful syntheses of eighty-eight otherwise difficult to access compounds in up to 99% yields, including the unprecedented 2-heteroarylethenesulfonyl fluorides, and 1,3-dienylsulfonyl fluorides.[+] These authors contributed equally.Supporting information for this article is given via a link at the end of the document. By employing three highly connective molecules, sulfuryl fluoride (SO 2 F 2 ), [1] thionyl tetrafluoride (O=SF 4 ), [2] and ethenesulfonyl fluoride (CH 2 =CH-SO 2 F, ESF, 1), [1], [3], [4] we are able to readily gain SuFEx-abilities for the compounds from nature's nucleophile pool or from the petrochemicals, and finally achieve functions in service of multiple disciplines [5], [6] via catalytic SuFEx protocols ( Figure 1a). Searching for new S VI -F functional groups and developing reliable methods for their installations are considered the major challenge for evolving the current SuFEx chemistry. HHS Public AccessESF, among the three irreplaceable scaffolds of SuFEx chemistry, is unique for its versatile reactivity. We have demonstrated ESF as an essential building block to prepare the otherwise difficult to access compounds, 2-arylethenesulfonyl fluorides, through a Heck-Matsuda process [ Figure 1b(1)]. [7] 2-Arylethenesulfonyl fluorides represent a rare family of selectively addressable bifunctional electrophiles. Sulfonyl fluorides and vinyl sulfonates (or sulfone) can be readily prepared from 2-arylethenesulfonyl fluorides, via Michael addition and SuFEx, respectively, which are both important classes of electrophiles and potential covalent pharmacophores ( Figure 1c). [8]-[10] The latter provide permanent inhibition of target proteins, which is of special interest for us. [11] Among the 152 approved S VIcontaining drugs, [12] 96 (63%) of them are (hetero)aryl sulfonyl molecules [(Het)Ar-SO 2 -Q, including aryl sulfones, sulfonamides, sulfonic acids and sulfonate esters]. The vinylogous analogs [(Het)Ar-CH=CH-SO 2 -Q] are much less explored, but could be interesting. Rigosertib (Figure 1d), a Phase III drug candidate treating myelodisplastic syndrome, is first of this kind to show promising bioactivity. [13] It is reasonable to conclude from the above that general methods for the synthesis of 2-substituted ethenesulfonyl fluorides would open up access to a new and likely v...