Visible-Light-Induced Oxidative Generation of o-Quinone Methides for Inverse-Electron-Demand [4+2] Cycloaddition Reactions

Shoya Nohara; Suguru Iwai; Naoya Yamaguchi; Yosuke Asada; Yusuke Kamiyama; Yuta Tanaka; Kenta Tanaka; Yujiro Hoshino

doi:10.1055/a-2158-8648

Synlett, Table of Contents

Synlett 2023; 34(20): 2525-2529
DOI: 10.1055/a-2158-8648

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Special Issue Dedicated to Prof. Hisashi Yamamoto

Visible-Light-Induced Oxidative Generation of o-Quinone Methides for Inverse-Electron-Demand [4+2] Cycloaddition Reactions

Authors

Shoya Nohara

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Suguru Iwai

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Naoya Yamaguchi

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Yosuke Asada

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Yusuke Kamiyama

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Yuta Tanaka

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan
Kenta Tanaka∗

^bResearch Institute for Interdisciplinary Science, Okayama University, 3-1-1 Tsushimanaka, Kita-ku, Okayama 700-8530, Japan
Yujiro Hoshino∗

^aGraduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai, Hodogaya-ku, Yokohama 240-8501, Japan

Abstract

All articles of this category

Abstract

Organophotoredox-catalyzed oxidative generation of o-quinone methides (o-QMs) for inverse-electron-demand [4+2] cycloaddition reactions has been developed. One-electron oxidation of 2-(sulfanylmethyl)phenols by thioxanthylium photoredox catalyst generated o-QMs, which reacted with various styrenes to produce chromanes with high regioselectivity. This reaction offers a valuable approach for in situ generating o-QMs via one-electron oxidation process under irradiation with mild green light.

Key words

o-quinone methide - photoredox - visible light - chromane - [4+2] cycloaddition

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References

References and Notes

1a Bai W.-J, David JG, Feng Z.-G, Weaver MG, Wu K.-L, Pettus TR. R. Acc. Chem. Res. 2014; 47: 3655
1b Sharma A, Hazarika H, Gogoi P. J. Org. Chem. 2021; 86: 4883
1c Barta P, Fülöp F, Szatmári I. Beilstein J. Org. Chem. 2018; 14: 560
1d Singh MS, Nagaraju A, Anand N, Chowdhury S. RSC Adv. 2014; 4: 55924

2a Inoue T, Inoue S, Sato K. Chem. Lett. 1989; 18: 653
2b Chiba K, Sonoyama J, Tada M. J. Chem. Soc., Chem. Commun. 1995; 1381
2c Chiba K, Sonoyama J, Tada M. J. Chem. Soc., Perkin Trans. 1 1996; 1435
2d Chiba K, Yamaguchi Y, Tada M. Tetrahedron Lett. 1998; 39: 9035
2e Chiba K, Hirano T, Kitano Y, Tada M. Chem. Commun. 1999; 691
2f Uyanik M, Nishioka K, Kondo R, Ishihara K. Nat. Chem. 2020; 12: 353

3a Le T, Galmiche L, Masson G, Allaina C, Audebert P. Chem. Commun. 2020; 56: 10742
3b Lyu J, Claraz A, Retailleau P, Masson G. Org. Biomol. Chem. 2022; 20: 9593

4a Arumugam S, Popik VV. J. Am. Chem. Soc. 2011; 133: 5573
4b Fujiwara M, Sakamoto M, Komeyama K, Yoshida H, Takaki K. J. Heterocycl. Chem. 2015; 52: 59
4c Nakatani K, Higashida N, Saito I. Tetrahedron Lett. 1997; 38: 5005
4d Škalamera Đ, Mlinarić-Majerski K, Martin-Kleiner I, Kralj M, Wan P, Basarić N. J. Org. Chem. 2014; 79: 4390

5 Zhou F, Cheng Y, Liu X.-P, Chen J.-R, Xiao W.-J. Chem. Commun. 2019; 55: 3117

6a Tanaka K, Ueno K, Tanaka Y, Ohtsuka N, Asada Y, Kishimoto M, Sunaga S, Hoshino Y, Honda K. Synlett 2020; 31: 1197
6b Tanaka K, Kishimoto M, Asada Y, Hoshino Y, Honda K. J. Org. Chem. 2019; 84: 13858
6c Tanaka K, Kishimoto M, Ohtsuka N, Iwama Y, Wada H, Hoshino Y, Honda K. Synlett 2019; 30: 189
6d Tanaka K, Hoshino Y, Honda K. J. Synth. Org. Chem. Jpn. 2018; 76: 1341
6e Tanaka K, Kishimoto M, Hoshino Y, Honda K. Tetrahedron Lett. 2018; 59: 1841
6f Tanaka K, Sukekawa M, Shigematsu Y, Hoshino Y, Honda K. Tetrahedron 2017; 73: 6456
6g Tanaka K, Hoshino Y, Honda K. Heterocycles 2017; 95: 474
6h Tanaka K, Hoshino Y, Honda K. Tetrahedron Lett. 2016; 57: 2448
6i Tanaka K, Shigematsu Y, Sukekawa M, Hoshino Y, Honda K. Tetrahedron Lett. 2016; 57: 5914
6j Tanaka K, Sukekawa M, Hoshino Y, Honda K. Chem. Lett. 2018; 47: 440
6k Tanaka K, Sukekawa M, Kishimoto M, Hoshino Y, Honda K. Heterocycles 2019; 99: 145

7a Tanaka K, Asada Y, Hoshino Y. Chem. Commun. 2022; 58: 2476
7b Tanaka K, Kishimoto M, Tanaka Y, Kamiyama Y, Asada Y, Sukekawa M, Ohtsuka N, Suzuki T, Momiyama N, Honda K, Hoshino Y. J. Org. Chem. 2022; 87: 3319
7c Tanaka K, Iwama Y, Kishimoto M, Ohtsuka N, Hoshino Y, Honda K. Org. Lett. 2020; 22: 5207
7d Tanaka K, Asada Y, Hoshino Y, Honda K. Org. Biomol. Chem. 2020; 18: 8074
7e Tanaka K, Hoshino Y, Honda K. J. Jpn. Soc. Colour Mater. 2020; 93: 49
7f Tanaka K, Omata D, Asada Y, Hoshino Y, Honda K. J. Org. Chem. 2019; 84: 10669
7g Tanaka K, Tanaka Y, Kishimoto M, Hoshino Y, Honda K. Beilstein J. Org. Chem. 2019; 15: 2105
7h Tanaka K, Sukekawa M, Kishimoto M, Hoshino Y, Honda K. Tetrahedron Lett. 2018; 59: 3361

8a Selenski C, Pettus TR. R. J. Org. Chem. 2004; 69: 9196
8b Jones RM, Selenski C, Pettus TR. R. J. Org. Chem. 2002; 67: 6911
8c Marsini MA, Huang Y, Lindsey CC, Wu K.-L, Pettus TR. R. Org. Lett. 2008; 10: 1477

9 Since it was difficult to separate the diastereomers in our system, the diastereomeric ratio of 3 was determined by ¹H NMR analysis comparing the benzylic peaks at the C2 position of chroman. Each of the diastereomers of 3a was confirmed by comparison with the spectral data described in the literature, see: Pagar VV, Tseng C.-C, Liu R.-S. Chem. Eur. J. 2014; 20: 10519
10 Yamaguchi T, Sugiura Y, Yamaguchi E, Tada N, Ito A. Asian J. Org. Chem. 2017; 6: 432
11 2,4-Diphenylchoroman (3a): Typical Procedure 2-(Sulfanylmethyl)phenol (1a, 58.3 mg, 0.20 mmol), styrene (2a, 62.5 mg, 0.60 mmol), TXT (5.0 mg, 9.0 μmol, 5.0 mol%), DCE (2.0 mL), and TFE (2.0 mL) were added into an 8 mL borosilicate vial. The resulting solution was stirred at room temperature under air and green LED irradiation for 24 h. The desired cycloadduct 3a was isolated by column chromatography on silica gel (hexane/ethyl acetate = 50:1). (2S*,4R*)- and (2R*,4R*)-2,4-Diphenylchromane (3a) White solid (42.4 mg, 74% yield). ¹H NMR (500 MHz, CDCl₃): δ = 7.52–7.48 (m, 2 H) (major), 7.42–7.38 (m, 2 H) (mixture), 7.37–7.29 (m, 8 H) (mixture), 7.29–7.19 (m, 6 H) (mixture), 7.17–7.12 (m, 2 H) (mixture), 7.02 (ddd, J = 14.1, 7.9, 1.5 Hz, 2 H) (minor), 6.97–6.95 (m, 1 H) (major), 6.90 (td, J = 7.4, 1.1 Hz, 1 H) (minor), 6.83–6.76 (m, 2 H) (major), 5.23 (dd, J = 11.2, 2.1 Hz, 1 H) (major), 5.05 (dd, J = 10.5, 2.3 Hz, 1 H) (minor), 4.37 (q, J = 6.1 Hz, 1 H) (major), 4.25 (q, J = 2.9 Hz, 1 H) (mixture), 2.51–2.46 (m, 1 H) (minor), 2.42 (ddd, J = 13.7, 5.7, 2.1 Hz, 1 H) (major), 2.33–2.24 (m, 1 H) (major). ¹³C{¹H} NMR (126 MHz, CDCl₃) (mixture): δ = 155.5, 155.4, 146.0, 144.5, 141.4, 141.2, 130.8, 129.8, 128.6, 128.6, 128.4, 128.1, 128.0, 127.7, 126.8, 126.4, 126.1, 126.0, 125.7, 123.1, 120.6, 120.5, 117.0, 117.0, 78.1, 73.2, 43.5, 40.6, 40.2, 38.3.
12 Lyu J, Claraz A, Vitale MR, Allain C, Masson G. J. Org. Chem. 2020; 85: 12843
13 See the Supporting Information.

Supplementary Material

Supporting Information (PDF) (opens in new window)