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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.
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