Custom-Made Pyrene Photocatalyst-Promoted Desulfonylation of Arylethenyl Sulfones Using Green-Light-Emitting Diodes

Hikaru Watanabe; Kazuki Nakajima; Kento Ekuni; Ryota Edagawa; Yuta Akagi; Yasuhiro Okuda; Kan Wakamatsu; Akihiro Orita

doi:10.1055/s-0040-1706025

Synthesis, Inhaltsverzeichnis

Synthesis 2021; 53(17): 2984-2994
DOI: 10.1055/s-0040-1706025

special topic

Bond Activation – in Honor of Prof. Shinji Murai

Custom-Made Pyrene Photocatalyst-Promoted Desulfonylation of Arylethenyl Sulfones Using Green-Light-Emitting Diodes

Hikaru Watanabe

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Kazuki Nakajima

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Kento Ekuni

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Ryota Edagawa

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Yuta Akagi

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Yasuhiro Okuda

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

,

Kan Wakamatsu

^bDepartment of Chemistry, Okayama University of Science, 1-1, Ridai-cho, Kita-ku, Okayama 700-0005, Japan

,

Akihiro Orita ∗

^aDepartment of Applied Chemistry and Biotechnology, Okayama University of Science, 1-1, Ridai-cho, Kita-ku,Okayama 700-0005, Japan

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

The Sonogashira coupling of 1,3,6,8-tetrabromopyrene with 4-[(–)-β-citronellyloxy]phenylethyne was employed to synthesize 1,3,6,8-tetra[4-(citronellyloxy)phenylethynyl]pyrene. The pyrene derivative catalyzed the reductive desulfonylation of ethenyl sulfones via visible-light irradiation (514 nm green light-emitting diodes) in the presence of i-Pr₂NEt. The β-citronellyloxy groups provided the sufficient solubility to the highly π-expanded pyrene catalyst, and their polar oxygen functionalities enabled the easy separation of the catalyst from the products via column chromatography.

Keywords

desulfonylation - photocatalyst - pyrene - ethenyl sulfones - ethenes - green LED

Volltext

Referenzen

References

For selected reviews of bioactive sulfones, see:

1a Liu J, Zheng L. Adv. Synth. Catal. 2019; 361: 1710
1b Devendar P, Yang G.-F. Top. Curr. Chem. 2017; 375: 1
1c Ahmad I. Shagufta, Int. J. Pharm. 2015; 7: 19
1d Chen X, Hussain S, Parveen S, Zhang S, Yang Y, Zhu C. Curr. Med. Chem. 2012; 19: 3578

For selected reviews, see:

2a Review of sulfones: Simpkins NS. Sulfones in Organic Synthesis . Oxford; Pergamon Press: 1993
2b Qiu D, Lian C, Mao J, Fagnoni M, Protti S. J. Org. Chem. 2020; 85: 12813
2c Wu X, Zhu C. Acc. Chem. Res. 2020; 53: 1620
2d Guerrero-Robles MA, Vilchis-Reyes MA, Ramos-Rivera EM, Alvarado C. ChemistrySelect 2019; 4: 13698
2e Yadav D, Menon RS. Org. Biomol. Chem. 2020; 18: 365
2f Li Y, Fan Y. Synth. Commun. 2019; 49: 3227
2g Trost BM, Kalnmals CA. Chem. Eur. J. 2019; 25: 11193
2h Marcantoni E, Palmieri A, Petrini M. Org. Chem. Front. 2019; 6: 2142
2i Takahashi F, Nogi K, Yorimitsu H. Phosphorus, Sulfur Silicon Relat. Elem. 2019; 194: 742
2j Guo W, Tao K, Tan W, Zhao M, Zheng L, Fan X. Org. Chem. Front. 2019; 6: 2048

3 It is reported that the bond dissociation energies of C–SO₂ are 54–83 kcal/mol: Benson SW. Chem. Rev. 1978; 78: 23

Selected recent reviews and papers on C–C bond formations:

4a Crespi S, Fagnoni M. Chem. Rev. 2020; 120: 9790
4b Chatelain P, Sau A, Rowley CN, Moran J. Angew. Chem. Int. Ed. 2019; 58: 14959
4c Millius N, Lapointe G, Renaud P. Molecules 2019; 24: 4184
4d Zhang M-M, Liu F. Org. Chem. Front. 2018; 5: 3443
4e Nambo M, Yim JC.-H, Freitas LB. O, Tahara Y, Ariki ZT, Maekawa Y, Yokogawa D, Crudden CM. Nat. Commun. 2019; 10: 4528
4f Merchant RR, Edwards JT, Qin T, Kruszyk MM, Bi C, Che G, Bao D-H, Qiao W, Sun L, Collins MR, Fadeyi OO, Gallego GM, Mousseau JJ, Nuhant P, Baran PS. Science 2018; 360: 75

We also developed one-pot and one-shot syntheses of diarylethynes by using benzyl sulfones and aldehydes as starting compounds:

5a Xu F, Peng L, Shinohara K, Morita T, Yoshida S, Hosoya T, Orita A, Otera J. J. Org. Chem. 2014; 79: 11592
5b Orita A, Taniguchi H, Otera J. Chem. Asian J. 2006; 1: 430
5c Orita A, Miyamoto K, Nakashima M, Ye F, Otera J. Adv. Synth. Catal. 2004; 346: 767

6a Whalley DM, Duon HA, Greaney MF. Chem. Commun. 2020; 56: 11493
6b Chen Y, McNamara N, May O, Pillaiyar T, Blakemore DC, Ley SV. Org. Lett. 2020; 22: 5746
6c Watanabe H, Takemoto M, Adachi K, Okuda Y, Dakegata A, Fukuyama T, Ryu I, Wakamatsu K, Orita A. Chem. Lett. 2020; 49: 409
6d Wang Z.-J, Zheng S, Matsui JK, Lu Z, Molander GA. Chem. Sci. 2019; 10: 4389

7 Julia M, Paris JM. Tetrahedron Lett. 1973; 4833

8a Keck GE, Savin KA, Weglarz MA. J. Org. Chem. 1995; 60: 3194

For Julia–Lythgoe olefination using sulfoxides, see:

8b Pospíšil J, Pospíšil T, Markó IE. Org. Lett. 2005; 7: 2373

For catalytic HgCl₂/Mg-promoted Julia olefination, see:

8c Lee GH, Lee HK, Choi EB, Kim BT, Pak CS. Tetrahedron Lett. 1995; 36: 5607

For selected reviews, see:

9a Chatterjee B, Bera S, Mondal D. Tetrahedron: Asymmetry 2014; 25: 1
9b Zajc B, Kumar R. Synthesis 2010; 1822
9c Aïssa C. Eur. J. Org. Chem. 2009; 1831
9d Blakemore PR. J. Chem. Soc., Perkin Trans. 1 2002; 2563

10 More recently a practical direct olefination protocol of sulfones with alcohols using nickel catalyst was successfully reported (see also references cited therein): Waiba S, Das A, Barman MK, Maji B. ACS Omega 2019; 4: 708

Other reductive desulfonylations were also reported:

11a Electrochemical desulfonylation: Botrel A, Furet E, Fourets O, Pilard J-F. New J. Chem. 2000; 24: 815
11b Transition-metal-catalyzed desulfonylation: Clayden J, Cooney JJ. A, Julia M. J. Chem. Soc., Perkin Trans. 1 1995; 7
11c Clayden J, Julia M. J. Chem. Soc., Chem. Commun. 1993; 1682

12 We already reported the synthesis of 1,3,6,8-tetrakis((trimethylsilyl)ethynyl)pyrene and its optical properties: Xu F, Nishida T, Shinohara K, Peng L, Takezaki M, Kamada T, Akashi H, Nakamura H, Sugiyama K, Ohta K, Orita A, Otera J. Organometallics 2017; 36: 556

For selected reviews, see:

13a Möller MN, Denicola A. Free Radic. Biol. Med. 2018; 128: 137
13b Feng X, Hu J-Y, Redshaw C, Yamato T. Chem. Eur. J. 2016; 22: 11898
13c Mauritz KA. Mater. Sci. Eng. C 1998; C6: 121

14a Diring S, Camerel F, Donnio B, Dintzer T, Toffanin S, Capelli R, Muccini M, Ziessel R. J. Am. Chem. Soc. 2009; 131: 18177
14b Maeda H, Maeda T, Mizuno K, Fujimoto K, Shimizu H, Inouye M. Chem. Eur. J. 2006; 12: 824

15 For simplicity, the calculations were performed by using 1,3,6,8-tetra(4-methoxyphenylethynyl)pyrene.

16a Okamoto S, Tsujioka H, Sudo A. Chem. Lett. 2018; 47: 369
16b Okamoto S, Ariki R, Tsujioka H, Sudo A. J. Org. Chem. 2017; 82: 9731
16c Okamoto S, Kojiyama K, Tsujioka H, Sudo A. Chem. Commun. 2016; 52: 11339
16d See also ref. 6c.

17a The LUMO energy levels were calculated using the following equation: E _LUMO = –4.80–E _1/2 ^red [eV]: Liu S-Y, Shi M-M, Huang J-C, Jin Z-N, Hu X-L, Pan J-Y, Li H-Y, Jen AK.-Y, Chen H-Z. J. Mater. Chem. A 2013; 1: 2795
17b See also the Supporting Information for details.

18a Waiba S, Barman MK, Maji B. J. Org. Chem. 2019; 84: 973
18b Julia M, Launay M, Stacino J-P, Verpeaux J-N. Tetrahedron Lett. 1982; 23: 2465
18c See also ref. 8a.

19 Because of the poor solubility of 1 in MeCN, the addition of a small amount of THF was crucial. See the Supporting Information for more detail of the solubility of 1.
20 An absorption terminus of perylene was observed at 460 nm. See also the Supporting Information for details.
21 DFT calculations (B3LYP/6-31G(d)) indicated the LUMO levels of 2d and 2e at –1.57 and –1.87 eV, respectively. The lower LUMO level of 2e could explain its more rapid desulfonylation in the competitive reaction. See also the Supporting Information for details.

22a We also attempted a three-step integration in the transformations of benzyl sulfone to 3n, namely, in the synthesis of 2g/desulfonylation/Sonogashira coupling. Unfortunately, the desired enyne 3n was contaminated with a trace amount of 1,3-di(phenylethynyl)benzene, which was produced at the synthesis of 2g by the unexpected further elimination of sulfinic acid.
22b See ref. 5c.

23 When the crude product 2p was subjected to the 1/green LED protocol, the expected desulfonylation did not emerge with 2p remaining untouched.

24a Fang J-K, An D-L, Wakamatsu K, Ishikawa T, Iwanaga T, Toyota S, Matsuo D, Orita A, Otera J. Tetrahedron Lett. 2010; 51: 917
24b See also the Supporting Information for details.

25a Although 6. and 6+ were more stable than 8. and 8+ by 2.2 kcal/mol and 5.7 kcal/mol, respectively, both 6. and 8. could be formed in the protonation stage of 2a.– because a difference of their HOFs (2.2 kcal/mol) was comparatively small and also because the formation of 8. might be kinetically favored than 6.. In fact, both 6. and 8. were described in the existing research. For instance, see ref. 16 and also the following paper: Chatterjee A, König B. Angew. Chem. Int. Ed. 2019; 58: 14289
25b See also the Supporting Information for the DFT calculations of their HOFs.

26 Huo C, He X, Chan TH. J. Org. Chem. 2008; 73: 8583
27 Xu HJ, Zhao YQ, Zhou XF. J. Org. Chem. 2011; 76: 8036
28 Kumar S, Pandey AK, Singh R, Singh KN. Eur. J. Org. Chem. 2018; 5942
29 Hang T, Chen T, Han LB. J. Org. Chem. 2018; 83: 2959
30 Zhang X, Liu A, Chen W. Org. Lett. 2008; 10: 3849

Zusatzmaterial

Supporting Information