Synlett 2020; 31(01): 77-82
DOI: 10.1055/s-0039-1691488
letter
© Georg Thieme Verlag Stuttgart · New York

Rhodium(III)-Catalyzed Regioselective C7-Allylation of Indazoles

Jiyou Huo
,
Hongshun Yuan
,
Lanting Xu
,
Xianhua Pan
This work was supported by the Shanghai Sailing Program (17YF1418900).
Further Information

Publication History

Received: 05 October 2019

Accepted after revision: 31 October 2019

Publication Date:
19 November 2019 (online)


Abstract

An efficient rhodium-catalyzed regioselective C–H allylation of N,N-diisopropylcarbamoyl indazoles with allylic carbonates as allylating agents has been developed. This methodology provides facile access to C7-allylated indazoles with high regioselectivity, ample substrate scope and broad functional group tolerance.

Supporting Information

Primary Data

 
  • References and Notes

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  • 19 Preparation of 3aa; Typical Procedure: To a 10 mL dry Schlenk tube with a stirring bar, indazole substrate 1a (0.2 mmol), [RhCp*Cl2]2 (6.2 mg, 5 mol%), Cu(OAc)2·H2O (20 mg, 50 mol%), AgNTf2 (15.5 mg, 20 mol%), and 4Å MS (100 mg) were added. The tube was evacuated and backfilled with nitrogen before allyl methyl carbonate 2a (116 μL, 1.0 mmol) and 1,2,3-trichloropropane (1.0 mL) were added. The reaction mixture was stirred at 65 °C for 24 h. After cooling to room temperature, the reaction mixture was purified by chromatography on silica with a gradient eluent of petroleum ether and ethyl acetate to give the corresponding product. 7-Allyl-N,N-diisopropyl-1H-indazole-1-carboxamide (3aa): Yield: 82% (46.7 mg); white solid. 1H NMR (500 MHz, CDCl3): δ = 8.07 (s, 1 H), 7.61 (d, J = 7.9 Hz, 1 H), 7.27 (d, J = 7.1 Hz, 1 H), 7.19 (t, J = 7.5 Hz, 1 H), 6.06–6.00 (m, 1 H), 5.07 (d, J = 10.1 Hz, 1 H), 4.96 (d, J = 17.2 Hz, 1 H), 4.12 (brs, 1 H), 3.77 (d, J = 4.7 Hz, 2 H), 3.61 (brs, 1 H), 1.56 (brs, 6 H), 1.26 (brs, 6 H). 13C NMR (125 MHz, CDCl3): δ = 151.62, 139.15, 136.55, 136.18, 128.91, 125.84, 124.68, 122.73, 119.02, 116.28, 51.36, 46.29, 36.71, 20.59, 20.08. HRMS (ESI): m/z [M + H]+ calcd for C17H24N3O+: 286.19139; found: 286.19119.