Photoinduced Metal-Free Arylboration of Unactivated Alkenes: Synthesis of Indoline Boronic Ester

Ji Lu; Yangsen He; Lixu Ren; Daling Li; Xianchao Pan; Lin Yang; Jun Wang; Siping Wei; Jun Wei

doi:10.1055/a-2184-5014

Synlett, Table of Contents

Synlett 2024; 35(12): 1399-1404
DOI: 10.1055/a-2184-5014

letter

Photoinduced Metal-Free Arylboration of Unactivated Alkenes: Synthesis of Indoline Boronic Ester

Ji Lu‡

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Yangsen He‡

^bDepartment of Pharmacy, West China Hospital Sichuan University, Jintang Hospital, Chengdu, Sichuan 610400, P. R. of China

,

Lixu Ren

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Daling Li

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Xianchao Pan

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Lin Yang

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Jun Wang

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Siping Wei

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

,

Jun Wei∗

^aGreen Pharmaceutical Technology Key Laboratory of Luzhou, School of Pharmacy, Southwest Medical University, Luzhou 646000, P. R. of China

^cState Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China

› Author Affiliations

Abstract

All articles of this category

Abstract

The environmentally benign synthesis of indoline boronic esters, especially through a way of arylboration to alkenes, remains a challenge due to the use of transition metals or high-temperature conditions. We described a photoinduced metal-free arylboration of unactivated alkenes for the synthesis of indoline boronic esters and 1,2,3,4-tetrahydroquinoline boronic ester in good yields. This approach showed good compatibility and great efficiency for a range of allylphenylamines as well as alkylamine. Remarkably, this transformation also suggested that the base is not necessary for photosensitizer-free diboron reagent mediated mild generation of aryl radical. Furthermore, compared to previously reported methods, this approach is mild and environmentally benign.

Key words

arylboration - photoinduced - indoline boronic ester - metal-free - unactivated alkenes

Full Text

References

References and Notes

1a Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
1b Dimitrijevic E, Taylor MS. ACS Catal. 2013; 3: 945
1c Tellis JC, Primer DN, Molander GA. Science 2014; 345: 433
1d Wen Y, Deng C, Xie J, Kang X. Molecules 2019; 24: 101
1e Tian Y.-M, Guo X.-N, Braunschweig H, Radius U, Marder TB. Chem. Rev. 2021; 121: 3561
1f Marotta A, Adams CE, Molloy JJ. Angew. Chem. Int. Ed. 2022; 61: e202207067

2a Volochnyuk DM, Gorlova AO, Grygorenko OO. Chem. Eur. J. 2021; 27: 15277
2b Grygorenko OO, Volochnyuk DM, Vashchenko BV. Eur. J. Org. Chem. 2021; 6478
2c Messner K, Vuong B, Tranmer GK. Pharmaceuticals 2022; 15: 264

3a Li D, Zhang H, Wang Y. Chem. Soc. Rev. 2013; 42: 8416
3b Kawai S, Saito S, Osumi S, Yamaguchi S, Foster AS, Spijker P, Meyer E. Nat. Commun. 2015; 6: 8098
3c Tanaka K, Gon M, Ito S, Ochi J, Chujo Y. Coord. Chem. Rev. 2022; 472: 214779

4a Wade CR, Broomsgrove AE. J, Aldridge S, Gabbaï FP. Chem. Rev. 2010; 110: 3958
4b Dai K, Zheng Y, Wei W. Adv. Funct. Mater. 2021; 31: 2008632

5a Yang K, Song Q. Org. Lett. 2016; 18: 5460
5b Zhang P, Xing M, Guan Q, Zhang J, Zhao Q, Zhang C. Org. Lett. 2019; 21: 8106
5c Bai X, Zheng W, Ge S, Lu Y. Org. Lett. 2022; 24: 3080
5d Zou C, Wu H, Ji Y, Zhang P, Cui H, Huang G, Zhang C. Chin. J. Chem. 2022; 40: 2437

6a Liang R.-X, Chen R.-Y, Zhong C, Zhu J.-W, Cao Z.-Y, Jia Y.-X. Org. Lett. 2020; 22: 3215
6b Wu F.-P, Gu X.-W, Geng H.-Q, Wu X.-F. Chem. Sci. 2023; 14: 2342

7a Logan KM, Sardini SR, White SD, Brown MK. J. Am. Chem. Soc. 2018; 140: 159
7b Chen L.-A, Lear AR, Gao P, Brown MK. Angew. Chem. Int. Ed. 2019; 58: 10956
7c Wang W, Ding C, Pang H, Yin G. Org. Lett. 2019; 21: 3968
7d Sardini SR, Lambright AL, Trammel GL, Omer HM, Liu P, Brown MK. J. Am. Chem. Soc. 2019; 141: 9391
7e Lambright AL, Liu Y, Joyner IA, Logan KM, Brown MK. Org. Lett. 2021; 23: 612
7f Meng X, Zhu L, Liang J, Shi H, Lv J, Wang M, Zhang L, Wang C. Org. Lett. 2022; 24: 6962

8a Smith KB, Brown MK. J. Am. Chem. Soc. 2017; 139: 7721
8b Sardini SR, Brown MK. J. Am. Chem. Soc. 2017; 139: 9823
8c Huang Y, Brown MK. Angew. Chem. Int. Ed. 2019; 58: 6048
8d Bergmann AM, Dorn SK, Smith KB, Logan KM, Brown MK. Angew. Chem. Int. Ed. 2019; 58: 1719
8e Simlandy AK, Lyu M.-Y, Brown MK. ACS Catal. 2021; 11: 12815
8f Dorn SK, Brown MK. ACS Catal. 2022; 12: 2058
8g Trammel GL, Kannangara PB, Vasko D, Datsenko O, Mykhailiuk P, Brown MK. Angew. Chem. Int. Ed. 2022; 61: e202212117

9 Semba K, Ohtagaki Y, Nakao Y. Org. Lett. 2016; 18: 3956
10 Vachhani DD, Butani HH, Sharma N, Bhoya UC, Shahb AK, Van der Eycken EV. Chem. Commun. 2015; 51: 14862
11 Wei F, Wei L, Zhou L, Tung C.-H, Ma Y, Xu Z. Asian J. Org. Chem. 2016; 5: 971
12 Kuang Z, Li B, Song Q. Chem. Commun. 2018; 54: 34

13a Kim H, Lee C. Angew. Chem. Int. Ed. 2012; 51: 12303
13b Nguyen J, D’Amato E, Narayanam J, Stephenson CR. J. Nat. Chem. 2012; 4: 854
13c Revo G, McCallum T, Morin M, Gagosz F, Barriault L. Angew. Chem. Int. Ed. 2013; 52: 13342
13d Devery JJ. III, Nguyen JD, Dai C, Stephenson CR. J. ACS Catal. 2016; 6: 5962
13e Yang C, Mehmood F, Lam TL, Chan SL.-F, Wu Y, Yeung C.-S, Guan X, Li K, Chung CY.-S, Zhou C.-Y, Zou T, Che C.-M. Chem. Sci. 2016; 7: 3123
13f Yang X, Liu W, Li L, Wei W, Li C.-J. Chem. Eur. J. 2016; 22: 15252
13g Michelet B, Deldaele C, Kajouj S, Moucheron C, Evano G. Org. Lett. 2017; 19: 3576
13h Caiuby CA. D, Ali A, Santana VT, de S Lucas FW, Santos MS, Corrêa AG, Nascimento OR, Jiang H, Paixão MW. RSC Adv. 2018; 8: 12879
13i Grübel M, Jandl C, Bach T. Synlett 2019; 30: 1825
13j Zidan M, McCallum T, Swann R, Barriault L. Org. Lett. 2020; 22: 8401
13k Li Y, Ying F, Fu T, Yang R, Dong Y, Lin L, Han Y, Liang D, Long X. Org. Biomol. Chem. 2020; 18: 5660
13l Bellotti P, Koy M, Gutheil C, Heuvel S, Glorius F. Chem. Sci. 2021; 12: 1810
13m Shon J.-H, Kim D, Rathnayake MD, Sittel S, Weaver J, Teets TS. Chem. Sci. 2021; 12: 4069
13n Smoleń S, Wincenciuk A, Drapała O, Gryko D. Synthesis 2021; 53: 1645
13o Marchese AD, Durant AG, Reid CM, Jans C, Arora R, Lautens M. J. Am. Chem. Soc. 2022; 144: 20554
13p Rezazadeh S, Martin MI, Kim RS, Yap GP. A, Rosenthal J, Watson DA. J. Am. Chem. Soc. 2023; 145: 4707
13q Li P.-S, Teng Q.-Q, Chen M. Chem. Commun. 2023; 59: 10620

14 Ye Y, Lin Y, Mao N.-D, Yang H, Ye X.-Y, Xie T. Org. Biomol. Chem. 2022; 20: 9255
15 Wu Y, Wu L, Zhang Z.-M, Xu B, Liu Y, Zhang J. Chem. Sci. 2022; 13: 2021

16a Cheng Y, Mück-Lichtenfeld C, Studer A. Angew. Chem. Int. Ed. 2018; 57: 16832
16b Yan G, Huang D, Wu X. Adv. Synth. Catal. 2018; 360: 1039
16c Tian Y.-M, Guo X.-N, Krummenacher I, Wu Z, Nitsch J, Braunschweig H, Radius U, Marder TB. J. Am. Chem. Soc. 2020; 142: 18231
16d Shu C, Noble A, Aggarwal VK. Nature 2020; 586: 714
16e Lai D, Ghosh S, Hajra A. Org. Biomol. Chem. 2021; 19: 4397
16f Zheng D, Jana K, Alasmary FA, Daniliuc CG, Studer A. Org. Lett. 2021; 23: 7688
16g Sarkar S, Wagulde S, Jia X, Gevorgyan V. Chem 2022; 8: 3096
16h Hazra S, Mahato S, Das KK, Panda S. Chem. Eur. J. 2022; 28: e202200556
16i Shiozuka A, Sekine K, Toki T, Kawashima K, Mori T, Kuninobu Y. Org. Lett. 2022; 24: 4281
16j Pan L, Deckert MM, Cooke MV, Bleeke AR, Laulhé S. Org. Lett. 2022; 24: 6466
16k Li B, Wang K, Yue H, Drichel A, Lin J, Su Z, Rueping M. Org. Lett. 2022; 24: 7434
16l Shang Z.-H, Pan J, Wang Z, Zhang Z.-X, Wu J. Eur. J. Org. Chem. 2023; 26: e202201379
16m Yamamoto Y, Ogawa A. Molecules 2023; 28: 787

17 Cheng Y, Mück-Lichtenfeld C, Studer A. J. Am. Chem. Soc. 2018; 140: 6221

18a Procedure for the Synthesis of Compound 2a To a Schlenk tube were added 1a (0.2 mmol) and bis(catecholato)diboron (61.8 mg, 1.3 equiv). The reaction vessel was evacuated and backfilled with argon for three times. Dimethylformamide (2.0 mL) was added. The reaction mixture was stirred under blue LEDs (30 W) irradiation at room temperature for 36 h. A solution of pinacol (95.0 mg, 4.0 equiv) in triethylamine (0.3 mL, 11.2 equiv) was added to the mixture. After 3 h, water (5 mL) was added, and the aqueous layer was extracted with ethyl acetate (5 × 3 mL). The combined organic layers were dried over magnesium sulfate, filtered, and concentrated. The product was purified by flash column chromatography on silica gel with PE/EtOAc = 10:1 as eluent to give product 2a in 84% yield.
18b Analytical Data of 2a ¹H NMR (400 MHz, CDCl₃): δ = 7.68 (d, J = 8.2 Hz, 2 H), 7.60 (d, J = 8.1 Hz, 1 H), 7.22 (d, J = 8.2 Hz, 2 H), 7.17 (t, J = 7.7 Hz, 1 H), 7.08 (d, J = 7.4 Hz, 1 H), 6.97 (t, J = 7.4 Hz, 1 H), 4.13 (t, J = 9.7 Hz, 1 H), 3.48 (dd, J = 10.4, 7.5 Hz, 1 H), 3.34–3.26 (m, 1 H), 2.36 (s, 3 H), 1.22 (s, 6 H), 1.19 (s, 6 H), 1.14 (dd, J = 16.2, 5.2 Hz, 1 H), 0.80 (dd, J = 16.1, 9.3 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.9, 141.4, 137.3, 134.1, 129.6, 127.7, 127.4, 124.0, 123.6, 114.7, 83.5, 57.6, 35.9, 24.9, 24.7, 21.6, 17.0 (br)* (*the carbon attached to boron is broadened due to quadrupolar relaxation). HRMS (ESI⁺): m/z calcd for C₂₂H₂₈BNO₄S [M + H]⁺: 414.1905; found: 414.1902.
18c Analytical Data of 2g<¹H NMR (400 MHz, CDCl₃): δ = 7.64 (d, J = 8.2 Hz, 2 H), 7.55 (dd, J = 8.8, 4.5 Hz, 1 H), 7.23 (d, J = 8.1 Hz, 2 H), 6.87 (td, J = 8.8, 2.5 Hz, 1 H), 6.80 (dd, J = 8.2, 1.9 Hz, 1 H), 4.14 (dd, J = 10.7, 9.1 Hz, 1 H), 3.49 (dd, J = 10.8, 7.5 Hz, 1 H), 3.33–3.08 (m, 1 H), 2.38 (s, 3 H), 1.23 (s, 6 H), 1.21 (s, 6 H), 1.06 (dd, J = 16.2, 5.6 Hz, 1 H), 0.76 (dd, J = 16.2, 9.0 Hz, 1 H). ¹³C NMR (101 MHz, CDCl₃): δ = 159.83 (d, J = 242.0 Hz), 144.1, 139.70 (d, J = 8.0 Hz), 137.44 (d, J = 2.0 Hz), 133.7, 129.7, 127.4, 116.01 (d, J = 8.5 Hz), 114.16 (d, J = 23.5 Hz), 111.46 (d, J = 24.0 Hz), 83.6, 58.0, 36.0 (d, J = 1.6 Hz), 24.9, 24.7, 21.6, 16.7 (br)* (*the carbon attached to boron is broadened due to quadrupolar relaxation). ¹⁹F NMR (376 MHz, CDCl₃): δ = –119.33. HRMS (ESI⁺): m/z calcd for C₂₂H₂₇BFNO₄S [M + H]⁺: 432.1811; found: 432.1810.
18d Analytical Data of 2r ¹H NMR (400 MHz, CDCl₃): δ = 7.64 (dd, J = 8.2, 6.4 Hz, 2 H), 7.53 (dd, J = 8.0, 4.7 Hz, 1 H), 7.16 (d, J = 8.0 Hz, 2 H), 7.12–7.08 (m, 1 H), 7.01 (t, J = 7.4 Hz, 1 H), 6.91– 6.85 (m, 1 H), 3.89 (td, J = 10.1, 2.7 Hz, 1 H), 3.71 (dd, J = 10.2, 7.0 Hz, 0.43 H), 3.56 (dd, J = 10.5, 7.0 Hz, 0.69 H), 3.38–3.33 (m, 0.69 H), 3.25 (dd, J = 15.6, 6.5 Hz, 0.43 H), 1.29 (tt, J = 14.6, 7.4 Hz, 1 H), 1.14 (d, J = 12.2 Hz, 7.5 H), 0.99 (d, J = 18.4 Hz, 4.4 H), 0.80 (d, J = 7.6 Hz, 1.3 H), 0.60 (d, J = 7.6 Hz, 1.9 H). ¹³C NMR (101 MHz, CDCl₃): δ = 143.9, 143.8, 142.3, 142.1, 134.8, 134.7, 134.1, 133.9, 129.6, 127.7, 127.4, 127.4, 125.0, 124.3, 123.4, 123.0, 114.1, 83.4, 83.2, 55.0, 53.3, 42.0, 41.2, 24.9, 24.7, 24.6, 24.5, 21.6, 20.6 (br)* (*the carbon attached to boron is broadened due to quadrupolar relaxation), 12.3, 10.3. HRMS (ESI⁺): m/z calcd for C₂₃H₂₀BNO₄S [M + H]⁺: 428.2061; found: 428.2061.

Supplementary Material

Supporting Information