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DOI: 10.1055/a-2293-3370
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Visible-Light-Catalyzed Regioselective Arylcarboxylation of Allenes with CO2

Xianming Zhang
a   Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361001, Fujian, P. R. of China
,
Zhenqiang Zhang∗
b   Yunnan Precious Metals Laboratory Company, Ltd., Kunming 650106, Yunnan, P. R. of China
,
Zhuangping Zhan∗
a   Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361001, Fujian, P. R. of China
› Author AffiliationsFinancial support from Open Project of Yunnan Precious Metals Laboratory Co., Ltd. (No. 2023050267), and Science and Technology Projects of Yunnan Precious Metals Laboratory Co., Ltd. (No. 2022050232) is gratefully acknowledged.
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Abstract

A visible-light-catalyzed arylcarboxylation of allenes with CO2 was developed using [Ir(ppy)2(dtbbpy)]PF6 (ppy = 2-phenylpyridine; dtbbpy = 4,4′-di-tert-butyl-2,2′-bipyridine) as a photocatalyst to synthesis β-aryl β,γ-unsaturated carboxylic acids. This multicomponent protocol proceeds in an atom-economical way with exclusive regioselectivity. Preliminary mechanistic experiments suggested that allylic carbanion species are the key intermediates.

Key words

photocatalysis - allenes - arylcarboxylation - regioselectivity - carbon dioxide

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2293-3370.
  • Supporting Information


Publication History

Received: 12 March 2024

Accepted after revision: 22 March 2024

Accepted Manuscript online:
22 March 2024

Article published online:
09 April 2024

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  • References and Notes

    • 1a Gooßen LJ, Rodríguez N, Gooßen K. Angew. Chem. Int. Ed. 2008; 47: 3100
      CrossrefPubMed
    • 1b Majumdar N. ACS Catal. 2022; 12: 8291
      Crossref
    • 2a Ran C.-K, Liao L.-L, Gao T.-Y, Gui Y.-Y, Yu D.-G. Curr. Opin. Green Sustainable Chem. 2021; 32: 100525
      Crossref
    • 2b Ye J.-H, Ju T, Huang H, Liao L.-L, Yu D.-G. Acc. Chem. Res. 2021; 54: 2518
      CrossrefPubMed
  • 3 Romero NA, Nicewicz DA. Chem. Rev. 2016; 116: 10075
    CrossrefPubMed

      • For selected examples and reviews of carboxylations using CO2 as a C1 source, see:
    • 4a Cao G.-M, Hu X.-L, Liao L.-L, Yan S.-S, Song L, Chruma JJ, Gong L, Yu D.-G. Nat. Commun. 2021; 12: 3306
      CrossrefPubMed
    • 4b Ran C.-K, Xiao H.-Z, Liao L.-L, Ju T, Zhang W, Yu D.-G. Natl. Sci. Open 2023; 2: 20220024 ; DOI: DOI: 10.1360/nso/20220024.
      Crossref
    • 4c Lan J, Lu X, Ren B, Duo F, Niu X, Si J. Org. Biomol. Chem. 2024; 22: 682
      CrossrefPubMed
    • 4d Zhang W, Chen Z, Jiang YX, Liao LL, Wang W, Ye JH, Yu DG. Nat. Commun. 2023; 14: 3529
      CrossrefPubMed
    • 5a Wang H, Gao Y, Zhou C, Li G. J. Am. Chem. Soc. 2020; 142: 8122
      CrossrefPubMed
    • 5b Hou J, Ee A, Cao H, Ong HW, Xu JH, Wu J. Angew. Chem. Int. Ed. 2018; 57: 17220
      CrossrefPubMed
    • 5c Yin Z.-B, Ye J.-H, Zhou W.-J, Zhang Y.-H, Ding L, Gui Y.-Y, Yan S.-S, Li J, Yu D.-G. Org. Lett. 2018; 20: 190
      CrossrefPubMed
    • 5d Ye J.-H, Miao M, Huang H, Yan S.-S, Yin Z.-B, Zhou W.-J, Yu D.-G. Angew. Chem. Int. Ed. 2017; 56: 15416
      CrossrefPubMed
  • 6 Hahm H, Baek D, Kim D, Park S, Ryoo JY, Hong S. Org. Lett. 2021; 23: 3879
    CrossrefPubMed
  • 7 Ju T, Zhou Y.-Q, Cao K.-G, Fu Q, Ye J.-H, Sun G.-Q, Liu X.-F, Chen L, Liao L.-L, Yu D.-G. Nat. Catal. 2021; 4: 304
    Crossref
  • 8 Zeng J.-H, Du D.-T, Liu B.-E, Zhang Z.-Q, Zhan Z.-P. J. Org. Chem. 2023; 88: 14789
    CrossrefPubMed
  • 9 Gao C, Zeng J, Zhang X, Liu Y, Zhan Z.-p. Org. Lett. 2023; 25: 3146
    CrossrefPubMed
  • 10 Photocatalyzed Arylcarboxylation of Allenes with CO2: General Procedure An oven-dried 10 mL Schlenk tube equipped with a magnetic stirrer bar was charged with the appropriate allene 1 (0.2 mmol, 1 equiv, if solid), DABCO (0.1 mmol, 0.5 equiv), K2CO3 (0.5 mmol, 2.5 equiv), HCOONa (0.4 mmol, 2 equiv), and Ir[(ppy)2dtbbpy]PF6 (5 mol%). The tube was sealed and degassed by three cycles of vacuum evacuation and subsequent backfilling with CO2. Subsequently, the appropriate allene 1 (0.2 mmol, 1 equiv, if liquid), the appropriate aryl iodide 2 (0.4 mmol, 2 equiv), and anhyd DMSO (2 mL) were added. The tube was placed under a blue LED (λ = 450 nm, 20 W) and irradiated for 24 h at r.t. The mixture was then acidified with 2 N aq HCl (1 mL) and quenched with H2O. It was then extracted with EtOAc (×3) and the combined organic layers were dried (MgSO4) and concentrated under reduced pressure. The crude product was purified by column chromatography [silica gel, hexane–EtOAc (5:1 to 1:1)] or by preparative TLC (hexane–EtOAc, 1:1). 3,4,4-Triphenylbut-3-enoic acid (3a) Prepared by following the general procedure and purified by column chromatography [silica gel, hexane–EtOAc (3:1)] to give a white solid; yield: 27 mg (43%). 1H NMR (400 MHz, CDCl3): δ = 7.38–7.27 (m, 5 H), 7.19–7.10 (m, 5 H), 7.09–6.99 (m, 3 H), 6.96–6.88 (m, 2 H), 3.58 (s, 2 H). 13C NMR (101 MHz, CDCl3): δ = 177.23, 143.75, 142.66, 142.21, 141.36, 131.80, 130.75, 129.80, 129.52, 128.58, 128.10, 127.64, 127.42, 126.87, 126.50, 41.57. HRMS (ESI): m/z [M + H]+ calcd for C22H19O2: 315.1380; found: 315.1382.