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Synlett 2023; 34(05): 451-456
DOI: 10.1055/a-1916-2937
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Special Edition Thieme Chemistry Journals Awardees 2022

Stereoselective Pd-Catalyzed Remote Hydroamination of Skipped Dienes with Azoles

Han-Zhe Miao
a   Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
,
Yang Liu
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
,
Ye-Wei Chen
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
,
Han-Yu Lu
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
,
Jian Li  ∗
a   Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China
,
Guo-Qiang Lin∗
a   Department of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
,
Zhi-Tao He  ∗
b   CAS Key Laboratory of Synthetic Chemistry of Natural Substances, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Shanghai, 200032, P. R. of China
c   School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, P. R. of China
› Author AffiliationsWe acknowledge the Science and Technology Commission of ­Shanghai Municipality (22ZR1475200), the Shanghai Rising-Star program (20QA1411300), the National Natural Science Foundation of China (NSFC 22071262, 22101296, 21871284, 91956113), the CAS Key Laboratory of Synthetic Chemistry of Natural Substances, and the Shanghai Institute of Organic Chemistry for financial support.
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Abstract

A novel palladium-catalyzed stereoselective remote ­hydroamination reaction is disclosed. A series of azoles and skipped dienes undergo the migratory allylic C–H amination in good yields and selectivities. A desymmetric migratory azolation process is also developed to highlight the reliability of the transformation. Preliminary mechanistic experiments corroborate the designed metal walking and allylic substitution cascade strategy via Pd–H catalysis, different from prior ligand-to-ligand hydrogen transfer pathway for conjugated dienes.

Key words

skipped diene - remote hydroamination - palladium ­hydride - azoles - migratory allylic C–H functionalization

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1916-2937.
  • Supporting Information


Publication History

Received: 15 July 2022

Accepted after revision: 02 August 2022

Accepted Manuscript online:
02 August 2022

Article published online:
02 September 2022

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  • 19 General Procedure for Palladium-Catalyzed Remote Hydroamination with AzolesIn a nitrogen-filled glovebox, Pd(PCy3)2Cl2 (7.4 mg, 0.010 mmol), L12 (4.2 mg, 0.010 mmol), NaBArF 4 (9.8 mg, 0.011 mmol), and dry PhCF3 (0.20 mL) were added to a 10 mL Schlenk tube and stirred at room temperature for 10 min. Then the remote diene 1 (0.20 mmol), nucleophile 2 (0.30 mmol), and dry Et3N (84 μL, 0.60 mmol) were added to the solution, and the resulting mixture was stirred at 80 °C for 24 h. After this time, the crude mixture was cooled down to room temperature, diluted with EtOAc (2 mL), filtered through Celite, condensed, and purified by flash column chromatography to afford product pure 3.(E)-1-(1-Phenylhex-1-en-3-yl)-1H-pyrazole (3a)Colorless oil, 75% yield. 1H NMR (400 MHz, CDCl3): δ = 7.55 (d, J = 1.8 Hz, 1 H), 7.45 (d, J = 2.3 Hz, 1 H), 7.37–7.35 (m, 2 H), 7.31–7.28 (m, 2 H), 7.25–7.21 (m, 1 H), 6.47 (d, J = 15.9 Hz, 1 H), 6.39 (dd, J = 15.9, 6.8 Hz, 1 H), 6.27 (t, J = 2.1 Hz, 1 H), 4.92–4.84 (m, 1 H), 2.20–2.08 (m, 1 H), 2.00–1.89 (m, 1 H), 1.40–1.19 (m, 2 H), 0.95 (t, J = 7.4 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 139.1, 136.3, 131.9, 129.0, 128.6, 128.0, 127.8, 126.6, 105.3, 64.3, 37.3, 19.4, 13.8. HRMS (EI): m/z [M]+ calcd for C15H18N2 +: 226.1470; found: 226.1465.