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. 2022 May 30;13(24):7347-7354.
doi: 10.1039/d2sc02205b. eCollection 2022 Jun 22.

RhodiumIII-catalyzed remote difunctionalization of arenes assisted by a relay directing group

Lincong Sun  1 , Yuyao Zhao  1 , Bingxian Liu  1 , Junbiao Chang  1 , Xingwei Li  1   2
Affiliations

RhodiumIII-catalyzed remote difunctionalization of arenes assisted by a relay directing group

Lincong Sun et al. Chem Sci. .

Abstract

Rhodium-catalyzed diverse tandem twofold C-H bond activation reactions of para-olefin-tethered arenes have been realized, with unsaturated reagents such as internal alkynes, dioxazolones, and isocyanates being the coupling partner as well as a relay directing group which triggers cyclization of the para-olefin group under oxidative or redox-neutral conditions. The reaction proceeded via initial ortho-C-H activation assisted by a built-in directing group in the arene, and the ortho-incorporation of the unsaturated coupling partner simultaneously generated a relay directing group that allows sequential C-H activation at the meta-position and subsequent cyclization of the para-olefins. The overall reaction represents C-C or N-C difunctionalization of the arene with the generation of diverse 2,3-dihydrobenzofuran platforms. The catalytic system proceeded with good efficiency, simple reaction conditions, and broad substrate scope. The diverse transformations of the products demonstrated the synthetic utility of this tandem reaction.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Metal-catalyzed selective C–H activation strategies.
Scheme 2
Scheme 2. Metal-catalyzed synthesis of 2,3-dihydrobenzofuran.
Scheme 3
Scheme 3. Substrate scope of alkynesa. a Reaction conditions: 1a (0.20 mmol), alkyne (0.26 mmol), [RhCp*Cl2]2 (5 mol%), CsOPiv (0.10 mmol, 0.5 equiv.), AgOAc (0.46 mmol, 2.3 equiv.), and t-AmOH (2 mL), at 120 °C under air for 12 h, and isolated yield.
Scheme 4
Scheme 4. Substrate scope of arenesa. a Reaction conditions: arene (0.20 mmol), 2a (0.26 mmol), [RhCp*Cl2]2 (5 mol%), CsOPiv (0.10 mmol, 0.5 equiv.), AgOAc (0.46 mmol, 2.3 equiv.), and t-AmOH (2 mL), at 120 °C under air for 12 h, and isolated yield. b DCE (2 mL) was used.
Scheme 5
Scheme 5. Substrate scope of directing groupsa. a Reaction conditions: arene (0.20 mmol), 2a (0.24 mmol), [RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%), PivOH (1.0 eq.), AgOAc (2.3 eq.), 120 °C, air, 24 h, and isolated yield. b TFE (2.0 mL) was used and 100 °C. c (R)-Rh (2.5 mol%), AgSbF6 (10 mol%), PivOH (2.0 eq.) and MeOH (2.0 mL) were used, 80 °C, and 48 h. d NaOAc (1.0 eq.) and 1,4-dioxane (2.0 mL) were used and 80 °C. e MeOH (2.0 mL) was used. f AgF (2.3 eq.) and THF (2.0 mL) were used. g NaOAc (1.0 eq.) and THF (2.0 mL) were used. ht-AmOH (2.0 mL) was used.
Scheme 6
Scheme 6. Substrate scope of unsaturated reagents. Reaction conditions: a1a (0.20 mmol), 2 (0.26 mmol), [RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%), PivOH (0.40 mmol, 2.0 equiv.), and HFIP (2 mL), at 110 °C under air for 36 h, and isolated yield. b1a (0.20 mmol), 2 (0.24 mmol), [RhCp*Cl2]2 (5 mol%), AgSbF6 (20 mol%), AgOAc (0.20 mmol, 1.0 equiv.), and DCM (2 mL), at 75 °C under N2 for 24 h, and isolated yield.
Scheme 7
Scheme 7. Synthetic transformations of compounds 3. Reaction conditions: (1) 3, 1-(triisopropylsilyl)ethynyl-1,2-benziodoxol-3(1H)-one (TIPS-EBX), [RhCp*Cl2]2, AgSbF6, MeOH, 60 °C, and 24 h. (2) 3, 3-phenyl-1,4,2-dioxazol-5-one (2zb), [RhCp*Cl2]2, AgSbF6, DCE, 80 °C, and 24 h. (3) 3, 3-diazopentane-2,4-dione, [RhCp*Cl2]2, AgSbF6, KOAc, DCE, 80 °C, N2, and 24 h. (4) 3, 1-isocyanato-4-methylbenzene, [RhCp*Cl2]2, AgSbF6, DCM, 80 °C, N2, and 12 h. (5) 3, 1,2-diphenylethyne, [RhCp*Cl2]2, AgSbF6, AgOTf, AgOAc, MeOH, 120 °C, N2, and 24 h.
Scheme 8
Scheme 8. Preliminary mechanistic studies.
Scheme 9
Scheme 9. Plausible mechanism.
See this image and copyright information in PMC

References

    1. For selected reviews of transition-metal-catalyzed C–H functionalization, see:

    2. McMurray L. O'Hara F. Gaunt M. J. Chem. Soc. Rev. 2011;40:1885–1898. doi: 10.1039/C1CS15013H. - DOI - PubMed
    3. Cho S. H. Kim J. Y. Kwak J. Chang S. Chem. Soc. Rev. 2011;40:5068–5083. doi: 10.1039/C1CS15082K. - DOI - PubMed
    4. Ackermann L. Chem. Rev. 2011;111:1315–1345. doi: 10.1021/cr100412j. - DOI - PubMed
    5. Li B.-J. Shi Z.-J. Chem. Soc. Rev. 2012;41:5588–5598. doi: 10.1039/C2CS35096C. - DOI - PubMed
    6. Arockiam P. B. Bruneau C. Dixneuf P. H. Chem. Rev. 2012;112:5879–5918. doi: 10.1021/cr300153j. - DOI - PubMed
    7. Shi Z. Koester D. C. Boultadakis-Arapinis M. Glorius F. J. Am. Chem. Soc. 2013;135:12204–12207. doi: 10.1021/ja406338r. - DOI - PubMed
    8. Chen Z. Wang B. Zhang J. Yu W. Liu Z. Zhang Y. Org. Chem. Front. 2015;2:1107–1295. doi: 10.1039/C5QO00004A. - DOI
    9. Song G. Li X. Acc. Chem. Res. 2015;48:1007–1020. doi: 10.1021/acs.accounts.5b00077. - DOI - PubMed
    10. Gensch T. Hopkinson M. N. Glorius F. Wencel-Delord J. Chem. Soc. Rev. 2016;45:2900–2936. doi: 10.1039/C6CS00075D. - DOI - PubMed
    11. Cera G. Ackermann L. Top. Curr. Chem. 2016;374:191. - PubMed
    12. Yang Y. Lan J. You J. Chem. Rev. 2017;117:8787–8863. doi: 10.1021/acs.chemrev.6b00567. - DOI - PubMed
    13. Hummel J. R. Boerth J. A. Ellman J. A. Chem. Rev. 2017;117:9163–9227. doi: 10.1021/acs.chemrev.6b00661. - DOI - PMC - PubMed
    14. Sambiagio C. Schönbauer D. Blieck R. Dao-Huy T. Pototschnig G. Schaaf P. Wiesinger T. Zia M. F. Wencel-Delord J. Besset T. Maes B. U. W. Schnürch M. Chem. Soc. Rev. 2018;47:6603–6743. doi: 10.1039/C8CS00201K. - DOI - PMC - PubMed
    15. Gandeepan P. Müller T. Zell D. Cera G. Warratz S. Ackermann L. Chem. Rev. 2019;119:2192–2452. doi: 10.1021/acs.chemrev.8b00507. - DOI - PubMed
    16. Dutta U. Maiti S. Bhattacharya T. Maiti D. Science. 2021;372 doi: 10.1126/science.abd5992. doi: 10.1126/science.abd5992. - DOI - PubMed
    17. Yu X. Zhang Z.-Z. Niu J.-L. Shi B.-F. Org. Chem. Front. 2022;9:1458–1484. doi: 10.1039/D1QO01884A. - DOI

    1. For selected examples, see:

    2. Ueura K. Satoh T. Miura M. Org. Lett. 2007;9:1407–1409. doi: 10.1021/ol070406h. - DOI - PubMed
    3. Ueura K. Satoh T. Miura M. J. Org. Chem. 2007;72:5362–5367. doi: 10.1021/jo070735n. - DOI - PubMed
    4. Rakshit S. Grohmann C. Besset T. Glorius F. J. Am. Chem. Soc. 2011;133:2350–2353. doi: 10.1021/ja109676d. - DOI - PubMed
    5. Guimond N. Gorelsky S. I. Fagnou K. J. Am. Chem. Soc. 2011;133:6449–6457. doi: 10.1021/ja201143v. - DOI - PubMed
    6. Hyster T. K. Knörr L. Ward T. R. Rovis T. Science. 2012;338:500–503. doi: 10.1126/science.1226132. - DOI - PMC - PubMed
    7. Hyster T. K. Dalton D. M. Rovis T. Chem. Sci. 2015;6:254–258. doi: 10.1039/C4SC02590C. - DOI - PMC - PubMed
    8. Semakul N. Jackson K. E. Paton R. S. Rovis T. Chem. Sci. 2017;8:1015–1020. doi: 10.1039/C6SC02587K. - DOI - PMC - PubMed
    9. Piou T. Romanov-Michailidis F. Romanova-Michaelides M. Jackson K. E. Semakul N. Taggart T. D. Newell B. S. Rithner C. D. Paton R. S. Rovis T. J. Am. Chem. Soc. 2017;139:1296–1310. doi: 10.1021/jacs.6b11670. - DOI - PMC - PubMed
    10. Ye B. Cramer N. Science. 2012;338:504–506. doi: 10.1126/science.1226938. - DOI - PubMed
    11. Wodrich M. D. Ye B. Gonthier J. F. Corminboeuf C. Cramer N. Chem.–Eur. J. 2014;20:15409–15418. doi: 10.1002/chem.201404515. - DOI - PubMed
    12. Wang D. Wang F. Song G. Li X. Angew. Chem., Int. Ed. 2012;51:12348–12352. doi: 10.1002/anie.201206918. - DOI - PubMed
    13. Qi Z. Wang M. Li X. Chem. Commun. 2014;50:9776–9778. doi: 10.1039/C4CC03627A. - DOI - PubMed
    14. Nguyen T. T. Grigorjeva L. Daugulis O. Angew. Chem., Int. Ed. 2018;57:1688–1691. doi: 10.1002/anie.201711968. - DOI - PMC - PubMed
    1. Leow D. Li G. Mei T.-S. Yu J.-Q. Nature. 2012;486:518–522. doi: 10.1038/nature11158. - DOI - PMC - PubMed
    1. Lee S. Lee H. Tan K. L. J. Am. Chem. Soc. 2013;135:18778–18781. doi: 10.1021/ja4107034. - DOI - PMC - PubMed
    2. Tang R.-Y. Li G. Yu J.-Q. Nature. 2014;507:215–220. doi: 10.1038/nature12963. - DOI - PMC - PubMed
    3. Yang G. Lindovska P. Zhu D. Kim J. Wang P. Tang R.-Y. Movassaghi M. Yu J.-Q. J. Am. Chem. Soc. 2014;136:10807–10813. doi: 10.1021/ja505737x. - DOI - PubMed
    4. Bera M. Modak A. Patra T. Maji A. Maiti D. Org. Lett. 2014;16:5760–5763. doi: 10.1021/ol502823c. - DOI - PubMed
    5. Bera M. Maji A. Sahoo S. K. Maiti D. Angew. Chem., Int. Ed. 2015;54:8515–8519. doi: 10.1002/anie.201503112. - DOI - PubMed
    6. Chu L. Shang M. Tanaka K. Chen Q. Pissarnitski N. Streckfuss E. Yu J.-Q. ACS Cent. Sci. 2015;1:394–399. doi: 10.1021/acscentsci.5b00312. - DOI - PMC - PubMed
    7. Patra T. Watile R. Agasti S. Naveen T. Maiti D. Chem. Commun. 2016;52:2027–2030. doi: 10.1039/C5CC09446A. - DOI - PubMed
    8. Li S. Cai L. Ji H. Yang L. Li G. Nat. Commun. 2016;7:10443–10450. doi: 10.1038/ncomms10443. - DOI - PMC - PubMed
    9. Maji A. Bhaskararao B. Singha S. Sunoj R. B. Maiti D. Chem. Sci. 2016;7:3147–3153. doi: 10.1039/C5SC04060D. - DOI - PMC - PubMed
    10. Bera M. Sahoo S. K. Maiti D. ACS Catal. 2016;6:3575–3579. doi: 10.1021/acscatal.6b00675. - DOI
    11. Xu H.-J. Lu Y. Farmer M. E. Wang H.-W. Zhao D. Kang Y.-S. Sun W.-Y. Yu J.-Q. J. Am. Chem. Soc. 2017;139:2200–2203. doi: 10.1021/jacs.6b13269. - DOI - PubMed
    12. Bag S. Jayarajan R. Mondal R. Maiti D. Angew. Chem., Int. Ed. 2017;56:3182–3186. doi: 10.1002/anie.201611360. - DOI - PubMed
    13. Bera M. Agasti S. Chowdhury R. Mondal R. Pal D. Maiti D. Angew. Chem., Int. Ed. 2017;56:5272–5276. doi: 10.1002/anie.201701579. - DOI - PubMed
    14. Dutta U. Modak A. Bhaskararao B. Bera M. Bag S. Mondal A. Lupton D. W. Sunoj R. B. Maiti D. ACS Catal. 2017;7:3162–3168. doi: 10.1021/acscatal.7b00247. - DOI
    15. Fang L. Saint-Denis T. G. Taylor B. L. H. Ahlquist S. Hong K. Liu S. S. Han L. L. Houk K. N. Yu J.-Q. J. Am. Chem. Soc. 2017;139:10702–10714. doi: 10.1021/jacs.7b03296. - DOI - PMC - PubMed
    16. Xu H.-J. Kang Y.-S. Shi H. Zhang P. Chen Y.-K. Zhang B. Liu Z.-Q. Zhao J. Sun W.-Y. Yu J.-Q. Lu Y. J. Am. Chem. Soc. 2019;141:76–79. doi: 10.1021/jacs.8b11038. - DOI - PubMed
    17. Achar T. K. Zhang X. Mondal R. Shanavas M. S. Maiti S. Maity S. Pal N. Paton R. S. Maiti D. Angew. Chem., Int. Ed. 2019;58:10353–10360. doi: 10.1002/anie.201904608. - DOI - PubMed
    18. Li S. Wang H. Weng Y. Li G. Angew. Chem., Int. Ed. 2019;58:18502–18507. doi: 10.1002/anie.201910691. - DOI - PubMed
    19. Porey S. Zhang X. Bhowmick S. Singh V. K. Guin S. Paton R. S. Maiti D. J. Am. Chem. Soc. 2020;142:3762–3774. doi: 10.1021/jacs.9b10646. - DOI - PubMed
    20. Bag S. S. K. Mondal A. Jayarajan R. Dutta U. Porey S. Sunoj R. B. Maiti D. J. Am. Chem. Soc. 2020;142:12453–12466. doi: 10.1021/jacs.0c05223. - DOI - PubMed
    21. Bag S. Jana S. Pradhan S. Bhowmick S. Goswami N. Sinha S. K. Maiti D. Nat. Commun. 2021;12:1393. doi: 10.1038/s41467-021-21633-2. - DOI - PMC - PubMed
    1. Wang X.-C. Gong W. Fang L.-Z. Zhu R.-Y. Li S. Engle K. M. Yu J.-Q. Nature. 2015;519:334–338. doi: 10.1038/nature14214. - DOI - PMC - PubMed