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Review
. 2023 May 3;13(20):13642-13654.
doi: 10.1039/d3ra01791e. eCollection 2023 May 2.

Aryl fluorosulfates: powerful and versatile partners in cross-coupling reactions

Shelesh Krishna Saraswat  1 , Ramanjaneyulu Seemaladinne  2 , Media Noori Abdullah  3 , Halim Zaini  4 , Nabeel Ahmad  5 , Nafis Ahmad  6 , Esmail Vessally  7
Affiliations
Review

Aryl fluorosulfates: powerful and versatile partners in cross-coupling reactions

Shelesh Krishna Saraswat et al. RSC Adv. .

Abstract

Aryl fluorosulfates are versatile building blocks in organic synthesis and have gained increasing attention in SuFEx (Sulfur Fluoride Exchange) click chemistry. They are easily and conveniently prepared from phenols using sulfuryl fluoride SO2F2 as a low-cost sulfonyl fluoride provider. Recently, they served as less toxic and more atom economical alternatives to triflates in an impressive number of carbon-carbon and carbon-heteroatom cross-coupling reactions. In this review, we summarize the current advances and developments in applying aryl fluorosulfates as electrophilic partners in cross-coupling reactions.

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Conflict of interest statement

There is no conflict of interest by any author.

Figures

Scheme 1
Scheme 1. Roth's synthesis of bi(hetero)aryls 3.
Scheme 2
Scheme 2. Dinuclear Pd-catalyzed coupling of (hetero)aryl fluorosulfonates 4 with organozinc reagents 5.
Scheme 3
Scheme 3. Triply selective sequential functionalization of (hetero)arenes 8 developed by Schoenebeck et al.
Scheme 4
Scheme 4. Pd-catalyzed coupling of aryl fluorosulfonates 10 with aryl- and vinyl-stannanes 11.
Scheme 5
Scheme 5. Suzuki–Miyaura coupling of aryl fluorosulfates 13 with aryl boronic acids 14 in water.
Scheme 6
Scheme 6. (a) Hanley's synthesis of biaryls 18; (b) Ni-catalyzed Suzuki reaction using aryl fluorosulfates 16.
Scheme 7
Scheme 7. Suzuki reaction of heteroaromatic fluorosulfonates 20 with (hetero)aryl boronic acids 21 catalyzed by Pd-PEPPSI-IPr.
Scheme 8
Scheme 8. (a) Suzuki reaction of aryl fluorosulfates 23 and potassium aryltrifluoroborates 24; (b) Li-Yuan's synthesis of terphenyls 29.
Scheme 9
Scheme 9. Suzuki reaction of (hetero)aryl fluorosulfates 30 and arylboronic acid pinacol esters 31.
Scheme 10
Scheme 10. (a) Synthesis of biaryls 35 through a one-pot sequential fluorosulfonation-Suzuki coupling approach developed by Li-Yuan's group; (b) mechanistic explanation for the formation of biaryls 35.
Scheme 11
Scheme 11. Synthesis of multisubstituted arenes 39via three-component reaction between aryl fluorosulfonates 36, boronic acids 37, and alkyl halides 38.
Scheme 12
Scheme 12. Selected examples of Pd-catalyzed Sonogashira cross-coupling of DNA-encoded (hetero)aryl fluorosulfates 40 with alkynes 41 reported by Yang-Lerner's research group.
Scheme 13
Scheme 13. Pd-catalyzed alkoxycarbonylation of aryl fhorosulfonates 43 developed by Roth.
Scheme 14
Scheme 14. Qin's synthesis of amides 48.
Scheme 15
Scheme 15. Continuous flow synthesis of aryl aldehydes 50 from aryl fluorosulfonates 49.
Scheme 16
Scheme 16. Ni-catalyzed carboxylation of (hetero)aryl fluorosulfates 51 using CO2.
Scheme 17
Scheme 17. Proposed mechanistic pathways for the reaction in Scheme 17.
Scheme 18
Scheme 18. Buchwald–Hartwig C–N coupling reaction between (hetero)aryl fluorosulfonates 53 with aniline 54.
Scheme 19
Scheme 19. Pd(PPh3)4-catalyzed amination of aryl fluorosulfonates 56 with aryl amines 57.
Scheme 20
Scheme 20. Ni- and Pd-catalyzed cross-coupling of (hetero)aryl fluorosulfonates 59 and hydrogen phosphoryl compounds 60.
Scheme 21
Scheme 21. Direct conversion of phenols to the corresponding aryl phosphonates though a sequential fluorosulfonation/C–P coupling approach.
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