Abstract

Both SF₅Cl and SF₅Br undergo smooth, high yield addition to alkenes and alkynes under the mild free radical chain reaction conditions of triethylborane initiation at low temperature, although the SF₅Br chemistry is somewhat limited by its competing high electrophilic reactivity with electron rich alkenes. The SF₅Cl addition reaction is relatively insensitive to a wide variety of non-allylic functionalities.

Graphical abstract

Both SF₅Cl and SF₅Br undergo smooth, high yield addition to alkenes and alkynes under the mild free radical chain reaction conditions of triethylborane initiation at low temperature.

Full-size image (2K)

Keywords: Pentafluorosulfanyl substituent; Free radical chain reaction; SF₅Cl; SF₅Br; Triethylborane initiation

Article Outline

1. Introduction

2. Results and discussion

2.1. SF₅Cl additions to alkenes

2.2. SF₅Cl additions to alkynes

2.3. Results using SF₅Br

2.4. Summary of addition results

2.5. Some chemistry of the SF₅Cl adducts

3. Experimental

3.1. General

3.2. Typical procedure for addition of SF₅Cl or SF₅Br to alkenes and alkynes [35]

3.2.1. 2-Chloro-1-pentafluorosulfanyloctane (1) [16]

3.2.2. 2-Chloro-1-pentafluorosulfanylhexane (2) [16] and [26]

3.2.3. 2-Chloro-3,3-dimethyl-1-pentafluorosulfanylbutane (3) [16]

3.2.4. 2-Chloro-2-ethyl-1-pentafluorosulfanylbutane (4) [16]

3.2.5. 4-Chloro-3-pentafluorosulfanylhexane (5) [16]

3.2.6. 1-Chloro-2-pentafluorosulfanylcyclohexane (6) [12] and [16]

3.2.7. 1-Chloro-1-(4-methylphenyl)-2-pentafluorosulfanylethane (7) [16]

3.2.8. 5-Chloro-6-pentafluorosulfanylhex-1-ene (8)

3.2.9. 4-Chloro-1-pentafluorosulfanylpent-2-ene (9)

3.2.10. 2-Chloro-3-pentafluorosulfanylprop-1-ene (10) [13]

3.2.11. 1-Chloro-2-pentafluorosulfanylethyl acetate (11) [14]

3.2.12. Ethyl 4-chloro-5-pentafluorosulfanylpentanoate (12)

3.2.13. 5-Chloro-6-pentafluorosulfanylhexan-2-one (13)

3.2.14. 9-Chloro-10-pentafluorosulfanyldecan-1-ol (14) [26]

3.2.15. 9-Chloro-10-pentafluorosulfanyldecyl acetate (15) [26]

3.2.16. 1-Bromo-9-chloro-10-pentafluorosulfanyldecane (16)

3.2.17. Methyl 3-chloro-4-pentafluorosulfanylbutanoate (17)

3.2.18. 2-Chloro-1-pentafluorosulfanylprop-2-yl acetate (18)

3.2.19. (E)-5-Chloro-4-pentafluorosulfanyloct-4-ene (19)

3.2.20. (E)-2-Chloro-1-pentafluorosulfanyloct-1-ene (20)

3.2.21. (E)-2-Chloro-1-pentafluorosulfanylhex-1-ene (21)

3.2.22. (E)-1-Chloro-2-pentafluorosulfanyl-1-phenylethene (22)

3.2.23. (1E,3Z)-1-Chloro-1,3-diphenyl-4-pentafluorosulfanylbuta-1,3-diene (23)

3.2.24. 1-Bromo-2-pentafluorosulfanylethane (24)

3.2.25. 2-Bromo-1-pentafluorosulfanylhexane (25) [24]

3.2.26. 2-Bromo-1-pentafluorosulfanylheptane (26)

3.2.27. 2-Bromo-1-pentafluorosulfanyloctane (27)

3.2.28. 2-Bromo-1-pentafluorosulfanylcyclohexane (28)

3.2.29. (E)-4-Bromo-5-pentafluorosulfanyloct-4-ene (29)

3.2.30. (E)-2-Bromo-1-pentafluorosulfanylprop-1-en-3-yl acetate (30)

3.2.31. 1-Bromo-1-phenyl-2-pentafluorosulfanylethene (31) [29]

3.3. 1,1-Dimethoxy-2-pentafluorosulfanylethane

3.4. Peroxymonosulfuric acid (Caro's acid) [36]

3.5. Methyl 2-pentafluorosulfanylacetate (32) [14]

3.6. Methyl 4-pentafluorosulfanyl but-2-enoate (33) [33]

3.7. 1-Pentafluorosulfanylpropan-2-one (34) [34]

3.8. 1-Pentafluorosulfanylhex-1-yne (35)

Acknowledgements

References