Stereoselective Pd-Catalyzed Remote Hydroamination of Skipped Dienes with Azoles

Han-Zhe Miao; Yang Liu; Ye-Wei Chen; Han-Yu Lu; Jian Li; Guo-Qiang Lin; Zhi-Tao He

doi:10.1055/a-1916-2937

Synlett, Inhaltsverzeichnis

Synlett 2023; 34(05): 451-456
DOI: 10.1055/a-1916-2937

cluster

Special Edition Thieme Chemistry Journals Awardees 2022

Stereoselective Pd-Catalyzed Remote Hydroamination of Skipped Dienes with Azoles

Han-Zhe Miao

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China

^bCAS 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

^bCAS 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

^bCAS 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

^bCAS 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 ∗

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China

,

Guo-Qiang Lin∗

^aDepartment of Chemistry, College of Science, Shanghai University, Shanghai 200444, P. R. of China

^bCAS 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 ∗

^bCAS 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

^cSchool of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, P. R. of China

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

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

Volltext

Referenzen

References and Notes
1 Taylor RD, MacCoss M, Lawson AD. G. J. Med. Chem. 2014; 57: 5845
2 Markham A, Duggan S. Drugs 2019; 79: 1813
3 Mesa RA, Yasothan U, Kirkpatrick P. Nat. Rev. Drug Discovery 2012; 11: 103
4 Cameron F, Sanford M. Drugs 2014; 74: 263

5a Zhang M, Guo X.-W, Zheng S.-C, Zhao X.-M. Tetrahedron Lett. 2012; 53: 6995
5b Kim SW, Schempp TT, Zbieg JR, Stivala CE, Krische MJ. Angew. Chem. Int. Ed. 2019; 58: 7762
5c Kang B, Zhang Q.-Y, Qu G.-R, Guo H.-M. Adv. Synth. Catal. 2020; 362: 1955

6 Zhuang H, Lu N, Ji N, Han F, Miao C. Adv. Synth. Catal. 2021; 363: 5461

For selected examples on transition-metal-catalyzed asymmetric 1,2-hydroaminations, see:

7a Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2000; 122: 9546
7b Löber O, Kawatsura M, Hartwig JF. J. Am. Chem. Soc. 2001; 123: 4366
7c Lutete LM, Kadota I, Yamamoto Y. J. Am. Chem. Soc. 2004; 126: 1622
7d Adamson NJ, Hull E, Malcolmson SJ. J. Am. Chem. Soc. 2017; 139: 7180
7e Long J, Wang P, Wang W, Li Y, Yin G. iScience 2019; 22: 369

8a Haydl AM, Xu K, Breit B. Angew. Chem. Int. Ed. 2015; 54: 7149
8b Hilpert LJ, Sieger SV, Haydl AM, Breit B. Angew. Chem. Int. Ed. 2019; 58: 3378

9a Bernar I, Fiser B, Blanco-Ania D, Gómez-Bengoa E, Rutjes FP. J. T. Org. Lett. 2017; 19: 4211
9b Alonso JM, Muñoz MP. Org. Lett. 2019; 21: 7639

10 Jiu AY, Slocumb HS, Yeung CS, Yang X.-H, Dong VM. Angew. Chem. Int. Ed. 2021; 60: 19660

For metal-involved chain-walking, see:

11a Sommer H, Juliá-Hernández F, Martin R, Marek I. ACS Cent. Sci. 2018; 4: 153
11b Dhungana RK, Sapkota RR, Niroula D, Giri R. Chem. Sci. 2020; 11: 9757
11c Li Y, Wu D, Cheng H.-G, Yin G. Angew. Chem. Int. Ed. 2020; 59: 7990
11d Janssen-Müller D, Sahoo B, Sun S.-Z, Martin R. Isr. J. Chem. 2020; 60: 195
11e Mei T.-S, Patel HH, Sigman MS. Nature 2014; 508: 340
11f Zhu S, Niljianskul N, Buchwald SL. Nat. Chem. 2016; 8: 144
11g Bruffaerts J, Pierrot D, Marek I. Nat. Chem. 2018; 10: 1164
11h Chen X, Cheng Z, Guo J, Lu Z. Nat. Commun. 2018; 9: 3939
11i Zhou F, Zhang Y, Xu X, Zhu S. Angew. Chem. Int. Ed. 2019; 58: 1754
11j Ross SP, Rahman AA, Sigman MS. J. Am. Chem. Soc. 2020; 142: 10516
11k Wang W, Ding C, Yin G. Nat. Catal. 2020; 3: 951
11l Zhang R, Yan X, Bai S.-T, Chen C, Nan B, Ma B, Wen J, Zhang X. Green Synth. Catal. 2022; 3: 40

12a Larock RC, Lu YD, Bain AC, Russell CE. J. Org. Chem. 1991; 56: 4589
12b Larock RC, Wang Y, Lu Y, Russell CA. J. Org. Chem. 1994; 59: 8107
12c Han X, Larock RC. Synlett 1998; 748
12d Larock RC, Han X. J. Org. Chem. 1999; 64: 1875
12e Wang Y, Dong X, Larock RC. J. Org. Chem. 2003; 68: 3090
12f Pang H, Wu D, Cong H, Yin G. ACS Catal. 2019; 9: 8555

13 Zhang Y, Shen H.-C, Li Y.-Y, Huang Y.-S, Han Z.-Y, Wu X. Chem. Commun. 2019; 55: 3769

14a Zhu D, Jiao Z, Chi YR, Gonçalves TP, Huang K.-W, Zhou JS. Angew. Chem. Int. Ed. 2020; 59: 5341
14b Zhu D, Xu W, Pu M, Wu Y.-D, Chi YR, Zhou JS. Org. Lett. 2021; 23: 7064

15 Yu R, Shanmugam R, Fang X. Angew. Chem. Int. Ed. 2020; 59: 21436
16 Chen Y.-W, Liu Y, Lu H.-Y, Lin G.-Q, He Z.-T. Nat. Commun. 2021; 12: 5626
17 See Mayr’s Database of Reactivity Parameters (accessed Aug 2, 2022): https://www.cup.lmu.de/oc/mayr/reaktionsdatenbank/fe/
18 Yang S.-Q, Wang Y.-F, Zhao W.-C, Lin G.-Q, He Z.-T. J. Am. Chem. Soc. 2021; 143: 7285
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), NaBAr^F 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.

Zusatzmaterial

Supporting Information