Photo-organocatalytic Synthesis of β-Keto Sulfonyl Fluorides via Radical Fluorosulfonylation of Vinyl Acetates

Peng Wang; Shao-Jie Li; Honghai Zhang; Na Yang; Saihu Liao

doi:10.1055/s-0041-1738692

Synlett, Table of Contents

Synlett 2023; 34(05): 471-476
DOI: 10.1055/s-0041-1738692

cluster

Special Edition Thieme Chemistry Journals Awardees 2022

Photo-organocatalytic Synthesis of β-Keto Sulfonyl Fluorides via Radical Fluorosulfonylation of Vinyl Acetates

Peng Wang‡

^aKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University, 350108 Fuzhou, P. R. of China

,

Shao-Jie Li‡

^aKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University, 350108 Fuzhou, P. R. of China

,

Honghai Zhang

^aKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University, 350108 Fuzhou, P. R. of China

,

Na Yang

^aKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University, 350108 Fuzhou, P. R. of China

,

Saihu Liao ∗

^aKey Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University), Fuzhou University, 350108 Fuzhou, P. R. of China

^bBeijing National Laboratory for Molecular Sciences (BNLMS), Beijing 100190, P. R. of China

› Author Affiliations

Abstract

All articles of this category

Abstract

A metal-free synthesis of useful β-keto sulfonyl fluorides has been established via radical fluorosulfonylation of ketone-derived vinyl acetates under photoredox organocatalysis by using 1-fluorosulfonyl benzoimidazolium (FABI) as the fluorosulfonyl radical source and oxygen-doped anthanthrene (ODA) as the photocatalyst. A series of aryl and alkyl β-keto sulfonyl fluorides as well as cyclic analogues can be readily obtained in moderate to high yields from widely available ketone starting materials.

Key words

sulfonyl fluorides - radical fluorosulfonylation - vinyl acetates - photoredox - organocatalysis

Full Text

References

References and Notes
1 Dong J, Krasnova L, Finn MG, Sharpless KB. Angew. Chem. Int. Ed. 2014; 53: 9430
2 Barrow AS, Smedley CJ, Zheng Q, Li S, Dong J, Moses JE. Chem. Soc. Rev. 2019; 48: 4731
3 Xu L, Dong J. Chin. J. Chem. 2020; 38: 414
4 Lee C, Cook AJ, Elisabeth JE, Friede NC, Sammis GM, Ball ND. ACS Catal. 2021; 11: 6578
5 Lou TS.-B, Willis MC. Nat. Rev. Chem. 2022; 6: 146
6 Epifanov M, Foth PJ, Gu F, Barrillon C, Kanani SS, Higman CS, Hein JE, Sammis GM. J. Am. Chem. Soc. 2018; 140: 16464
7 Meng G, Guo T, Ma T, Zhang J, Shen Y, Sharpless KB, Dong J. Nature 2019; 574: 86
8 Wang L, Cornella JA. Angew. Chem. Int. Ed. 2020; 59: 23510
9 Wei M, Liang D, Cao X, Luo W, Ma G, Liu Z, Li L. Angew. Chem. Int. Ed. 2021; 60: 7397
10 Smedley CJ, Homer JA, Gialelis TL, Barrow AS, Koelln RA, Moses JE. Angew. Chem. Int. Ed. 2022; 61: e202112375
11 Narayanan A, Jones LH. Chem. Sci. 2015; 6: 2650
12 Dalton SE, Campos S. ChemBioChem 2020; 21: 1080
13 Grygorenko OO, Volochnyuk DM, Vashchenko BV. Eur. J. Org. Chem. 2021; 6478
14 Jones LH. ACS Med. Chem. Lett. 2018; 9: 584
15 Jones LH, Kelly JW. RSC Med. Chem. 2020; 11: 10
16 Gao B, Zhang L, Zheng Q, Zhou F, Klivansky LM, Lu J, Liu Y, Dong J, Wu P, Sharpless KB. Nat. Chem. 2017; 9: 1083
17 Hmissa T, Zhang X, Dhumal NR, McManus GJ, Zhou X, Nulwala HB, Mirjafari A. Angew. Chem. Int. Ed. 2018; 57: 16005
18 Yang C, Flynn JP, Niu J. Angew. Chem. Int. Ed. 2018; 57: 16194
19 Liu Y, Wu H, Guo Y, Xiao J.-C, Chen Q.-Y, Liu C. Angew. Chem. Int. Ed. 2017; 56: 15432
20 Davies AT, Curto JM, Bagley SW, Willis MC. Chem. Sci. 2017; 8: 1233
21 Lou TS, Bagley SW, Willis MC. Angew. Chem. Int. Ed. 2019; 58: 18859
22 Laudadio G, Bartolomeu A. deA, Verwijlen LM. H. M, Cao Y, de Oliveira KT, Noël T. J. Am. Chem. Soc. 2019; 141: 11832
23 Zhong T, Yi J.-T, Chen Z.-D, Thuang Q.-C, Li Y.-Z, Lu G, Weng J. Chem. Sci. 2021; 12: 9359
24 Jin S, Haug GC, Trevino R, Nguyen VD, Arman HD, Larionov OV. Chem. Sci. 2021; 12: 13914
25 Qin HL, Zheng Q, Bare GA, Wu P, Sharpless KB. Angew. Chem. Int. Ed. 2016; 55: 14155
26 Zha GF, Zheng Q, Leng J, Wu P, Qin HL, Sharpless KB. Angew. Chem. Int. Ed. 2017; 56: 4849
27 Xu R, Xu T, Yang M, Cao T, Liao S. Nat. Commun. 2019; 10: 3752
28 Smedley CJ, Li G, Barrow AS, Gialelis TL, Giel M.-C, Ottonello A, Cheng Y, Kitamura S, Wolan DW, Sharpless KB, Moses JE. Angew. Chem. Int. Ed. 2020; 59: 12460
29 Frye NL, Daniliuc CG, Studer A. Angew. Chem. Int. Ed. 2022; 61: e202115593
30 Chen D, Nie X, Feng Q, Zhang Y, Wang Y, Wang Q, Huang L, Huang S, Liao S. Angew. Chem. Int. Ed. 2021; 60: 27271
31 Henkel T, Krügerke T, Seppelt K. Angew. Chem. 1990; 102: 1171
32 Nie X, Xu T, Song J, Devaraj A, Zhang B, Chen Y, Liao S. Angew. Chem. Int. Ed. 2021; 60: 3956
33 Nie X, Xu T, Hong Y, Zhang H, Mao C, Liao S. Angew. Chem. Int. Ed. 2021; 60: 22035
34 Nie X, Liao S. Synlett 2021; 401
35 Feng Q, Fu Y, Zheng Y, Liao S, Huang S. Org. Lett. 2022; 24: 3702
36 Cui J, Ke S, Zhao J, Wu S, Luo W, Xu S, Su X, Li Y. Org. Chem. Front. 2022; 9: 3540
37 Liao S, Wang P, Zhang H. Chinese Patent CN 113248444 A, ZL 202110597989.9 2021
38 Wang P, Zhang H, Nie X, Xu T, Liao S. Nat. Commun. 2022; 13: 3370
39 Synthesis of 3a: The ODA (0.3 mg, 0.001 mmol, 1 mol%) was weighed into a 10-mL oven-dried Schlenk tube equipped with a stirrer bar, followed by the addition of FABI (127.5 mg, 0.25 mmol). The tube was evacuated and backfilled with argon for three times, then 1a (0.1 mmol) and anhydrous 1,4-dioxane (4 mL, 25 mM) was added under argon flow. The reaction mixture was allowed to stir at room temperature under blue LED irradiation for 12 h, then it was directly concentrated in vacuo. The residue was purified by silica gel flash chromatography (0.05% AcOH in petroleum ether/EtOAc = 10:1) to give the corresponding desired product 3a (17.4 mg, 86%). ¹H NMR (500 MHz, CDCl₃): δ = 7.96 (dq, J = 8.7, 1.4 Hz, 2 H), 7.74–7.67 (m, 1 H), 7.56 (tt, J = 7.7, 1.6 Hz, 2 H), 5.01 (d, J = 2.3 Hz, 2 H). ¹³C NMR (126 MHz, CDCl₃): δ = 184.9, 135.4, 134.6 (d, J = 3.0 Hz), 129.4, 129.0, 57.6 (d, J = 15.7 Hz). ¹⁹F NMR (471 MHz, CDCl₃): δ = 63.0 Compound 3s: Yield: 19.2 mg (84%). ¹H NMR (400 MHz, CDCl₃): δ = 7.88 (d, J = 8.4 Hz, 2 H), 7.34 (d, J = 8.3 Hz, 2 H), 5.37 (m, 1 H), 2.45 (s, 3 H), 1.86 (d, J = 7.0 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 188.7, 146.5, 132.0 (d, J = 2.2 Hz), 130.1, 129.4, 61.7 (d, J = 12.8 Hz), 22.0, 13.9. ¹⁹F NMR (376 MHz, CDCl₃): δ = 50.8. HRMS (ESI): m/z calculated for C₁₀H₁₁FNaO₃S [M + Na]⁺ 253.0305; found: 253.0305. Compound 3x: Yield: 12.6 mg (60%). ¹H NMR (400 MHz, CDCl₃): δ = 4.38 (d, J = 3.2 Hz, 2 H), 2.69 (t, J = 7.2 Hz, 2 H), 1.65 (p, J = 7.2 Hz, 2 H), 1.38–1.22 (m, 6 H), 0.93–0.83 (m, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 194.7, 60.4 (d, J = 15.4 Hz), 43.6, 31.5, 28.5, 23.2, 22.5, 14.1. ¹⁹F NMR (376 MHz, CDCl₃): δ = 61.7.
40 Cheng P, Wang W, Wang L, Zeng J, Reiser O, Liang Y. Tetrahedron Lett. 2019; 60: 1408
41 Jiang H, Cheng Y, Zhang Y, Yu S. Eur. J. Org. Chem. 2013; 5485
42 Ma Q, Song J, Zhang X, Jiang Y, Ji L, Liao S. Nat. Commun. 2021; 12: 429
43 Roth HG, Romero NA, Nicewicz DA. Synlett 2016; 714

Supplementary Material

Supporting Information