Sulfonylation of organometallic reagents with arenesulfonyl fluorides: a simple one-step synthesis of sulfones

Frye, Leah L.; Sullivan, Eileen L.; Cusack, Kevin P.; Funaro, John M.

doi:10.1021/jo00028a053

Cited by 63 publications

(28 citation statements)

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“…Along with the greater barriers to attack at sulfur(VI), the high polarizability of the chlorine center in -SO 2 Cl and related groups makes it vulnerable to reductive attack (by both one-and two-electron pathways, depending on nucleophile and conditions), so that reactions with carbon nucleophiles usually give mixtures resulting from both sulfonylation and chlorination. Examples from the literature include reactions with organolithium reagents, [27] sulfur ylides, [28] phosphorous ylides, [29] and electrophilic aromatic substitution. [26,30] In all these cases, sulfonyl fluorides provide only sulfonylation outcomes.…”

Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt's unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.

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Section: Organic Sulfonyl Fluorides and Their Derivativesmentioning

confidence: 99%

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

et al. 2014

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“…In 1992, Frye and co‐workers reported a simple one‐step synthesis of sulfones from arenesulfonyl fluorides and organometallic reagents. Aryl sulfonyl fluorides reacted with tertiary organometallic reagents to form the respective sulfones, while secondary and primary organometallic reagents resulted in bis‐aryl sulfones (Scheme ) …”

Section: Applications Of Sfs In Organic Synthesismentioning

confidence: 99%

Sulfonyl Fluorides (SFs): More Than Click Reagents?

2018

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Sulfonyl fluoride (SF) containing substances are currently attracting enormous attention among practitioners of both chemical biology and synthetic organic chemistry. The groups of Jones and Liskamp have demonstrated the potential of sulfonyl fluorides as selective covalent inhibitors in studies related to drug discovery and chemical biology, respectively, in the last few years. The Sharpless group has extended the repertoire of “click‐reactions” to those involving sulfonyl fluorides, that is, sulfur–fluoride exchange (SuFEx), a development that quickly triggered the interest in this functional group in the community of synthetic organic chemists. In this microreview, we aim to give an account of the synthetic chemistry surrounding sulfonyl fluoride containing substances from a historical perspective to present day developments.

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“…Normally, alkynyl sulfone compounds prepared by this technique are used as intermediates for the synthesis of more complex molecules. Scheme shows the general methodology for the synthesis of alkynyl sulfones by means of this technique …”

Section: Synthesis By Nucleophilic Substitution Of Organolithium Compmentioning

confidence: 99%

Synthesis of Alkynyl Sulfones

et al. 2019

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Alkynyl sulfones are organic structures of high synthetic interest, since they can react with nucleophiles by conjugated addition (Michael addition) or through anti-Michael addition. Such interesting reactive properties make these compounds important intermediates in the synthesis of more complex organic molecules or naturally occurring products. Despite the use of alkynyl sulfones as starting materials (or intermediates), there was not a real interest in developing specific method-ologies for their synthesis. Therefore, the synthesis of alkynyl sulfones remained unchanged for a long time. It was not until the 1970s that studies focused on the development of new synthetic routes began to emerge. This Mini Review presents the advances and the state of the art of the synthesis of alkynyl sulfones. Methodologies described in the manuscript are classified according to the starting materials and reagents used. Moreover, every class is arranged in chronological order.

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Sulfonylation of organometallic reagents with arenesulfonyl fluorides: a simple one-step synthesis of sulfones

Cited by 63 publications

References 0 publications

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Sulfur(VI) Fluoride Exchange (SuFEx): Another Good Reaction for Click Chemistry

Sulfonyl Fluorides (SFs): More Than Click Reagents?

Synthesis of Alkynyl Sulfones

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