Visible-Light-Induced Photoredox Construction of Trifluoromethylated Quaternary All-Carbon Centers and Tertiary Alcohols via C(sp3)–Si Bond Cleavage

Dandan Ma; Lingna Chang; Yue Cai; Dachang Bai

doi:10.1055/s-0040-1720139

Synthesis, Inhaltsverzeichnis

Synthesis 2025; 57(07): 1295-1305
DOI: 10.1055/s-0040-1720139

feature

Visible-Light-Induced Photoredox Construction of Trifluoromethylated Quaternary All-Carbon Centers and Tertiary Alcohols via C(sp³)–Si Bond Cleavage

Dandan Ma

,

Lingna Chang

,

Yue Cai

,

Dachang Bai∗

Abstract

Alle Artikel dieser Rubrik

Abstract

The construction of trifluoromethylated quaternary carbon centers and tertiary alcohols is realized by organo-photoredox catalysis. The process proceeds via visible-light-induced C(sp³)–Si bond cleavage for the generation of α-trifluoromethylated benzyl radicals, which are readily trapped by electron-deficient alkenes with excellent regioselectivity for the construction of trifluoromethylated quaternary all-carbon centers. The α-difluoromethyl counterparts are also suitable for this radical conjugate addition. Furthermore, the in situ oxidation of these α-trifluoromethylated radicals with O₂ from air affords tertiary alcohols in high yields, which extends the Fleming–Tamao reaction to tertiary carbon systems.

Key words

visible-light-induced - trifluoromethylated quaternary carbon centers - tertiary alcohols - C(sp³)–Si bond cleavage - transition-metal-free

Volltext

Referenzen

References

1a Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications, 2nd ed. Wiley-VCH; Weinheim: 2013
1b Ni CF, Hu MY, Hu JB. Chem. Rev. 2015; 115: 765
1c Meanwell NA. J. Med. Chem. 2018; 61: 5822
1d Mei HB, Remete AM, Zou YP, Moriwaki H, Fustero S, Kiss L, Soloshonok VA, Han JL. Chin. Chem. Lett. 2020; 31: 2401
1e Johnson BM, Shu Y.-Z, Zhuo X, Meanwell NA. J. Med. Chem. 2020; 63: 6315

For selected reviews, see:

2a Nie J, Guo HC, Cahard D, Ma JA. Chem. Rev. 2011; 111: 455
2b Tomashenko OA, Grushin VV. Chem. Rev. 2011; 111: 4475
2c Furuya T, Kamlet AS, Ritter T. Nature 2011; 473: 470
2d Alonso C, Marigorta EM, Rubiales G, Palacios F. Chem. Rev. 2015; 115: 1847
2e Yang X, Wu T, Phipps RJ, Toste FD. Chem. Rev. 2015; 115: 826
2f Liu X, Xu C, Wang M, Liu Q. Chem. Rev. 2015; 115: 683
2g Qing FL, Liu XY, Ma JA, Shen QL, Song QL, Tang PP. CCS Chem. 2022; 4: 2518
2h Hirano K. Synthesis 2022; 54: 3708

For selected examples, see:

3a Chu LL, Qing FL. J. Am. Chem. Soc. 2010; 132: 7262
3b Hu M, Ni C, Hu J. J. Am. Chem. Soc. 2012; 134: 15257
3c Bai DC, Wang XL, Zheng GF, Li XW. Angew. Chem. Int. Ed. 2018; 57: 6633
3d Gao CF, Zhou Y, Ma H, Zhang Y, Nie J, Zhang FG, Ma JA. CCS Chem. 2022; 4: 3693
3e Liu J, Hao J, Shen QL. Chin. J. Org. Chem. 2023; 43: 1517
3f Liang HM, Wang Q, Zhou X, Zhang RY, Zhou M, Wei J, Ni CF, Hu JB. Angew. Chem. Int. Ed. 2024; 63: e202401091

For selected examples, see:

4a Liang Y, Fu GC. J. Am. Chem. Soc. 2015; 137: 9523
4b Gao X, Xiao YL, Wan X, Zhang X. Angew. Chem. Int. Ed. 2018; 57: 3187
4c Huang W, Hu M, Wan X, Shen Q. J. Am. Chem. Soc. 2019; 141: 11446
4d Lin TY, Pan Z, Tu YS, Zhu S, Wu HH, Liu Y, Li ZM, Zhang JL. Angew. Chem. Int. Ed. 2020; 59: 22957
4e Jiang C, Wang L, Zhang H, Chen P, Guo YL, Liu G. Chem 2020; 6: 2407
4f Min Y, Sheng J, Yu JL, Ni SX, Ma G, Gong H, Wang XS. Angew. Chem. Int. Ed. 2021; 60: 9947
4g Jiang XH, Tang PP. Chin. J. Org. Chem. 2021; 41: 2525
4h Hu M, Tan BB, Ge SZ. J. Am. Chem. Soc. 2022; 144: 15333
4i Zhu C, Zhang H, Liu Q, Chen K, Liu ZY, Feng C. ACS Catal. 2022; 12: 9410
4j Xu P, Fan W, Chen P, Liu G. J. Am. Chem. Soc. 2022; 144: 13468
4k Wu BB, Xu J, Bian KJ, Gao Q, Wang XS. J. Am. Chem. Soc. 2022; 144: 6543
4l Chen JY, Bai DC, Guo XL, Wang YY, Li XW. Chin. Chem. Lett. 2022; 33, 5056
4m Li YZ, Rao N, An L, Wan XL, Zhang YX, Zhang XG. Nat. Commun. 2022; 13: 5539
4n Lin D, Chen Y, Dong Z, Pei P, Ji H, Tai L, Chen LA. CCS Chem. 2023; 5: 1386
4o Wang R, Gao L, Zhou C, Zhang X. Chin. J. Org. Chem. 2023; 43: 1136
4p Liu SP, Yang Y, Song QM, Liu ZH, Lu Y, Wang ZJ, Sivaguru P, Bi XH. Nat. Chem. 2024; 16: 988
4q Wu F, Li X, Chang JB, Bai DC. Chin. Chem. Lett. 2024; 35: 109155
4r Wu F, Chang JB, Bai DC. Org. Lett. 2024; 26: 4953
4s Lu SY, Hu ZH, Wang D, Xu T. Angew. Chem. Int. Ed. 2024; 63: e202406064

For a selected review, see:

5a Wang SF, Wang WG. Chin. J. Org. Chem. 2020; 40: 1901

For selected examples, see:

5b Früh N, Togni A. Angew. Chem. Int. Ed. 2014; 53: 10813
5c Woźniak Ł, Murphy JJ, Melchiorre P. J. Am. Chem. Soc. 2015; 137: 5678
5d Granados A, Rivilla I, Cossío FP, Vallribera A. Chem. Eur. J. 2019; 25: 8214
5e Calvo R, Comas-Vives A, Togni A, Katayev D. Angew. Chem. Int. Ed. 2019; 58: 1447

For a selected review, see:

6a Deng YP, He JJ, Cao S, Qian XH. Chin. Chem. Lett. 2022; 33: 2363

For selected examples, see:

6b Kawai H, Okusu S, Tokunaga E, Sato H, Shiro M, Shibata N. Angew. Chem. Int. Ed. 2012; 51: 4959
6c Kawai H, Yuan Z, Kitayama T, Tokunaga E, Shibata N. Angew. Chem. Int. Ed. 2013; 52: 5575
6d Gao JR, Wu H, Xiang B, Yu W.-B, Han L, Jia Y.-X. J. Am. Chem. Soc. 2013; 135: 2983
6e Kwiatkowski P, Cholewiak A, Kasztelan A. Org. Lett. 2014; 16: 5930
6f Ye J.-H, Song L, Zhou W.-J, Ju T, Yin Z.-B, Yan S.-S, Zhang Z, Li J, Yu D.-G. Angew. Chem. Int. Ed. 2016; 55: 10022
6g Sanz-Marco A, Blay G, Vila C, Pedro JR. Org. Lett. 2016; 18: 3538
6h Ibáñez I, Kaneko M, Kamei Y, Tsutsumi R, Yamanaka M, Akiyama T. ACS Catal. 2019; 9: 6903

7a Trost BM, Debien L. J. Am. Chem. Soc. 2015; 137: 11606
7b Xu B, Zhang Z.-M, Liu B, Xu S, Zhou L.-J, Zhang J. Chem. Commun. 2017; 53: 8152
7c Rabasa-Alcañiz F, Torres J, Sánchez-Roselló M, Tejero T, Merino P, Fustero S, del Pozo C. Adv. Synth. Catal. 2017; 359: 3752
7d Xu S, Zhang Z.-M, Xu B, Liu B, Liu Y, Zhang J. J. Am. Chem. Soc. 2018; 140: 2272
7e Xu S, Liu B, Zhang Z.-M, Xu B, Zhang J. Chin. J. Chem. 2018; 36: 421
7f Bai X, Wu C, Ge S, Lu Y. Angew. Chem. Int. Ed. 2020; 59: 2764

8a Tsuchida K, Senda Y, Nakajima K, Nishibayashi Y. Angew. Chem. Int. Ed. 2016; 55: 9728
8b Punna N, Harada K, Shibata N. Chem. Commun. 2018; 54: 7171
8c Terashima K, Kawasaki-Takasuka T, Agou T, Kubota T, Yamazaki T. Chem. Commun. 2020; 56: 3031
8d Sun YT, Zhu DX, Rao XF, Xu MH. Org. Chem. Front. 2020; 7: 340
8e Zhang YL, Tanabe Y, Kuriyama S, Sakata K, Nishibayashi Y. Nat. Commun. 2023; 14: 859

9a Li XJ, Chen D, Gu HR, Lin XF. Chem. Commun. 2014; 50: 7538
9b Neves-Garcia T, Vélez A, Martínez-Ilarduya JM, Espinet P. Chem. Commun. 2018; 54: 11809
9c Gan XC, Zhang Q, Jia XS, Yin L. Org. Lett. 2018; 20: 1070

10a Stephenson CR. J, Yoon TP, MacMillan DW. C. Visible Light Photocatalysis in Organic Chemistry . Wiley-VCH; Weinheim: 2018

For selected reviews, see:

10b Zeitler K. Angew. Chem. Int. Ed. 2009; 48: 9785
10c Narayanam JM, Stephenson CR. J. Chem. Soc. Rev. 2011; 40: 102
10d Xuan J, Xiao W.-J. Angew. Chem. Int. Ed. 2012; 51: 6828
10e Zhao Y, Lv Y, Xia W. Chem. Rec. 2019; 19: 424
10f Wei Y, Zhou Q.-Q, Tan F, Lu L.-Q, Xiao W.-J. Synthesis 2019; 51: 3021
10g Jiang Y, Yin Y, Jiang Z. Chin. J. Org. Chem. 2024; 44: 1733

For selected examples, see:

11a Espelt LR, McPherson IS, Wiensch EM, Yoon TP. J. Am. Chem. Soc. 2015; 137: 2452
11b Silvi M, Verrier C, Rey YP, Buzzetti L, Melchiorre P. Nat. Chem. 2017; 9: 868
11c Khatun N, Kim MJ, Woo SK. Org. Lett. 2018; 20: 6239
11d Uygur M, Danelzika T, Mancheño OG. Chem. Commun. 2019; 55: 2980
11e Liu RF, Chia S, Goh Y, Cheo H, Fan B, Li RF, Zhou R, Wu J. Eur. J. Org. Chem. 2020; 10: 1459
11f Dong X, Li QY, Yoon TP. Org. Lett. 2021; 23: 5703

For a selected review, see:

12a Milligan JA, Phelan JP, Badir SO, Molander GA. Angew. Chem. Int. Ed. 2019; 58: 6152

For selected examples, see:

12b Zheng S, Chen Z, Hu Y, Xi X, Liao Z, Li W, Yuan W. Angew. Chem. Int. Ed. 2020; 59: 17910
12c Dong WZ, Badir SO, Zhang X, Molander GA. Org. Lett. 2021; 23: 4250
12d Zheng S, Wang W, Yuan W. J. Am. Chem. Soc. 2022; 144: 17776
12e Wang WL, Yan XY, Ye F, Zheng SL, Huang GP, Yuan WM. J. Am. Chem. Soc. 2023; 145: 23385

13a Hayamizu T, Ikeda M, Maeda H, Mizuno K. Org. Lett. 2001; 3: 1277
13b Montanaro S, Ravelli D, Merli D, Fagnoni M, Albini A. Org. Lett. 2012; 14: 4218
13c Jouffroy M, Primer DN, Molander GA. J. Am. Chem. Soc. 2016; 138: 475
13d Jackl MK, Legnani L, Morandi B, Bode JW. Org. Lett. 2017; 19: 4696
13e Li Q, Li X, Ling YF, Liu JX, Jun Y. ACS Catal. 2023; 13: 6879

14a Bai DC, Wu F, Chang LN, Wang MM, Wu H, Chang JB. Angew. Chem. Int. Ed. 2022; 61: e202114918
14b Bai DC, Zhong KB, Chang LN, Qiao Y, Wu F, Xu GQ, Chang JB. Nat. Commun. 2024; 15: 6360

15a Bai DC, Guo XL, Wang XH, Xu WJ, Cheng RS, Wei DH, Lan Y, Chang JB. Nat. Commun. 2024; 15: 2833
15b Bai DC, Guo YY, Ma DD, Guo XL, Wu H. Org. Lett. 2023; 25: 533

16a Tamao K, Akita M, Kumada M. J. Organomet. Chem. 1983; 254: 13
16b Magar SS, Fuchs PL. Tetrahedron Lett. 1991; 32: 7513

17a Virginie C, Claire B, Vincent G, Thierry O. Org. Lett. 2019; 21: 9094
17b Pavlenko NV, Peng S, Petrov V, Jackson A, Sun X, Sprague L, Yagupolskii YL. Eur. J. Org. Chem. 2020; 33: 5425

Zusatzmaterial