Manganese(I)-Catalyzed C–H Allylation of Tryptophans and Their Oligopeptides On Water

Julia Struwe; Tsuyoshi Oyama; Fabrice Gallou; Lutz Ackermann

doi:10.1055/a-2268-4678

Synlett, Table of Contents

Synlett 2024; 35(08): 903-907
DOI: 10.1055/a-2268-4678

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Special Issue dedicated to Keith Fagnou

Manganese(I)-Catalyzed C–H Allylation of Tryptophans and Their Oligopeptides On Water

Julia Struwe

^aInstitut für Organische und Biomolekulare Chemie, Wöhler-Forschungsinstitut für Nachhaltige Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany

,

Tsuyoshi Oyama

^aInstitut für Organische und Biomolekulare Chemie, Wöhler-Forschungsinstitut für Nachhaltige Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany

,

Fabrice Gallou∗

^bChemical & Analytical Development, Novartis Pharma AG, 4056 Basel, Switzerland

,

Lutz Ackermann ∗

^aInstitut für Organische und Biomolekulare Chemie, Wöhler-Forschungsinstitut für Nachhaltige Chemie, Georg-August-Universität Göttingen, Tammannstraße 2, 37077 Göttingen, Germany

^cGerman Center for Cardiovascular Research (DZHK), Potsdamer Straße 58, 10785, Berlin, Germany

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Abstract

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Abstract

The manganese(I)-catalyzed allylation of the amino acid tryptophan is realized under exceedingly mild conditions using water as a sustainable and non-hazardous reaction medium, instead of classical organic solvents, with great potential for green and sustainable chemistry. Synthetically useful α,β-unsaturated esters can be accessed by reaction with Morita–Baylis–Hillman (MBH) adducts following a fast C–H activation approach. The robustness of this procedure is reflected by kinetic analysis at different reaction temperatures and reduced catalyst loadings are employed.

Key words

C–H activation - on water - peptides - manganese catalysis - late-stage functionalization

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References

References and Notes
1 Lau JL, Dunn MK. Bioorg. Med. Chem. 2018; 26: 2700
2 Fosgerau K, Hoffmann T. Drug Discovery Today 2015; 20: 122
3 Guillemard L, Kaplaneris N, Ackermann L, Johansson MJ. Nat. Rev. Chem. 2021; 5: 522
4 Räder AF. B, Weinmüller M, Reichart F, Schumacher-Klinger A, Merzbach S, Gilon C, Hoffman A, Kessler H. Angew. Chem. Int. Ed. 2018; 57: 14414
5 Blaskovich MA. T. J. Med. Chem. 2016; 59: 10807
6 Bottecchia C, Noël T. Chem. Eur. J. 2019; 25: 26
7 Brandhofer T, García Mancheño O. Eur. J. Org. Chem. 2018; 6050
8 Lee HG, Lautrette G, Pentelute BL, Buchwald SL. Angew. Chem. Int. Ed. 2017; 56: 3177
9 Vinogradova EV, Zhang C, Spokoyny AM, Pentelute BL, Buchwald SL. Nature 2015; 526: 687
10 Rogge T, Kaplaneris N, Chatani N, Kim J, Chang S, Punji B, Schafer LL, Musaev DG, Wencel-Delord J, Roberts CA, Sarpong R, Wilson ZE, Brimble MA, Johansson MJ, Ackermann L. Nat. Rev. Methods Primers 2021; 1: 43
11 Gensch T, James MJ, Dalton T, Glorius F. Angew. Chem. Int. Ed. 2018; 57: 2296
12 Chu JC. K, Rovis T. Angew. Chem. Int. Ed. 2018; 57: 62
13 Lapointe D, Fagnou K. Chem. Lett. 2010; 39: 1118
14 Wang W, Lorion MM, Shah J, Kapdi AR, Ackermann L. Angew. Chem. Int. Ed. 2018; 57: 14700
15 Mendive-Tapia L, Preciado S, García J, Ramón R, Kielland N, Albericio F, Lavilla R. Nat. Commun. 2015; 6: 7160
16 Ruiz-Rodríguez J, Albericio F, Lavilla R. Chem. Eur. J. 2010; 16: 1124
17 Hou X, Kaplaneris N, Yuan B, Frey J, Ohyama T, Messinis AM, Ackermann L. Chem. Sci. 2022; 13: 3461
18 Schischko A, Kaplaneris N, Rogge T, Sirvinskaite G, Son J, Ackermann L. Nat. Commun. 2019; 10: 3553
19 Schischko A, Ren H, Kaplaneris N, Ackermann L. Angew. Chem. Int. Ed. 2017; 56: 1576
20 Li B, Li X, Han B, Chen Z, Zhang X, He G, Chen G. J. Am. Chem. Soc. 2019; 141: 9401
21 Zhang X, Lu G, Sun M, Mahankali M, Ma Y, Zhang M, Hua W, Hu Y, Wang Q, Chen J, He G, Qi X, Shen W, Liu P, Chen G. Nat. Chem. 2018; 10: 540
22 Yin X.-S, Qi W.-Y, Shi B.-F. Chem. Sci. 2021; 12: 13137
23 Zhan B.-B, Li Y, Xu J.-W, Nie X.-L, Fan J, Jin L, Shi B.-F. Angew. Chem. Int. Ed. 2018; 57: 5858
24 Chen G, Shigenari T, Jain P, Zhang Z, Jin Z, He J, Li S, Mapelli C, Miller MM, Poss MA, Scola PM, Yeung K.-S, Yu J.-Q. J. Am. Chem. Soc. 2015; 137: 3338
25 Liu T, Qiao JX, Poss MA, Yu J.-Q. Angew. Chem. Int. Ed. 2017; 56: 10924
26 Bai Z, Cai C, Yu Z, Wang H. Angew. Chem. Int. Ed. 2018; 57: 13912
27 Tran LD, Daugulis O. Angew. Chem. Int. Ed. 2012; 51: 5188
28 Reddy BV. S, Reddy LR, Corey EJ. Org. Lett. 2006; 8: 3391
29 Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192
30 Hu Y, Zhou B, Wang C. Acc. Chem. Res. 2018; 51: 816
31 Ruan Z, Sauermann N, Manoni E, Ackermann L. Angew. Chem. Int. Ed. 2017; 56: 3172
32 Jei BB, Yang L, Ackermann L. Chem. Eur. J. 2022; 28: e202200811
33 Kaplaneris N, Kaltenhäuser F, Sirvinskaite G, Fan S, De Oliveira T, Conradi L.-C, Ackermann L. Sci. Adv. 2021; 7: eabe6202
34 Kaplaneris N, Son J, Mendive-Tapia L, Kopp A, Barth ND, Maksso I, Vendrell M, Ackermann L. Nat. Commun. 2021; 12: 3389
35 Luo Z, Whitcomb CA, Kaylor N, Zhang Y, Zhang S, Davis RJ, Gunnoe TB. ChemCatChem 2021; 13: 260
36 Zhu W, Luo Z, Chen J, Liu C, Yang L, Dickie DA, Liu N, Zhang S, Davis RJ, Gunnoe TB. ACS Catal. 2019; 9: 7457
37 Kaplaneris N, Rogge T, Yin R, Wang H, Sirvinskaite G, Ackermann L. Angew. Chem. Int. Ed. 2019; 58: 3476
38 Wang W, Subramanian P, Martinazzoli O, Wu J, Ackermann L. Chem. Eur. J. 2019; 25: 10585
39 Prat D, Hayler J, Wells A. Green Chem. 2014; 16: 4546
40 Henderson RK, Jiménez-González C, Constable DJ. C, Alston SR, Inglis GG. A, Fisher G, Sherwood J, Binks SP, Curzons AD. Green Chem. 2011; 13: 854
41 Cortes-Clerget M, Yu J, Kincaid JR. A, Walde P, Gallou F, Lipshutz BH. Chem. Sci. 2021; 12: 4237
42 Hauk P, Wencel-Delord J, Ackermann L, Walde P, Gallou F. Curr. Opin. Colloid Interface Sci. 2021; 56: 101506
43 Gallou F. Chimia 2020; 74: 538
44 Steven A. Synthesis 2019; 51: 2632
45 Anastas P, Eghbali N. Chem. Soc. Rev. 2010; 39: 301
46 Anastas PT, Kirchhoff MM. Acc. Chem. Res. 2002; 35: 686
47 Lipshutz BH, Ghorai S. Aldrichimica Acta 2012; 45: 3
48 Lipshutz BH, Ghorai S, Abela AR, Moser R, Nishikata T, Duplais C, Krasovskiy A, Gaston RD, Gadwood RC. J. Org. Chem. 2011; 76: 4379
49 Cortes-Clerget M, Lee NR, Lipshutz BH. Nat. Protoc. 2019; 14: 1108
50 Borrego E, Caballero A, Pérez PJ. Organometallics 2022; 41: 3084
51 Sarathkumar S, Kavala V, Yao C.-F. Org. Lett. 2021; 23: 1960
52 Peng W, Liu Q, Yin F, Shi C, Ji L, Qu L, Wang C, Luo H, Kong L, Wang X. RSC Adv. 2021; 11: 8356
53 Mandal A, Garai B, Dana S, Bera R, Baidya M. Chem. Asian J. 2020; 15: 4009
54 Nie R, Lai R, Lv S, Xu Y, Guo L, Wang Q, Wu Y. Chem. Commun. 2019; 55: 11418
55 Chen X, Cui X, Bai L, Wang Y, Xie Y, Wang S, Zhai R, Zhao K, Kong D, Li Y. Asian J. Org. Chem. 2019; 8: 2209
56 Drev M, Grošelj U, Ledinek B, Perdih F, Svete J, Štefane B, Požgan F. Org. Lett. 2018; 20: 5268
57 Wu S, Wu X, Fu C, Ma S. Org. Lett. 2018; 20: 2831
58 Ali MA, Yao X, Sun H, Lu H. Org. Lett. 2015; 17: 1513
59 Ackermann L, Pospech J. Org. Lett. 2011; 13: 4153
60 Ackermann L. Org. Lett. 2005; 7: 3123
61 Dhawa U, Kaplaneris N, Ackermann L. Org. Chem. Front. 2021; 8: 4886
62 Kaplaneris N, Vilches-Herrera M, Wu J, Ackermann L. ACS Sustainable Chem. Eng. 2022; 10: 6871
63 Wei D, Lin G.-Q. Chin. J. Chem. 2024; 42: 533
64 Ackermann L. Acc. Chem. Res. 2020; 53: 84
65 Loup J, Dhawa U, Pesciaioli F, Wencel-Delord J, Ackermann L. Angew. Chem. Int. Ed. 2019; 58: 12803
66 Krell C, Schreiber R, Hueber L, Sciascera L, Zheng X, Clarke A, Haenggi R, Parmentier M, Baguia H, Rodde S, Gallou F. Org. Process Res. Dev. 2021; 25: 900
67 Butyl ((S)-2-((3-(2-((tert-Butoxycarbonyl)amino)-3-methoxy-3-oxopropyl)-1-(pyridin-2-yl)-1H-indol-2-yl)methyl)acrylate) (3a); Typical Procedure Tryptophan 1 (63.4 mg, 0.20 mmol, 1.00 equiv), MnBr(CO)₅ (5.5 mg, 20 μmol, 10 mol%) and NaOAc (4.9 mg, 60 μmol, 30 mol%) were placed in a 10 mL vial. The vial was then evacuated and filled with N₂ three times. Afterwards, the MBH adduct 2a (103 mg, 0.40 mmol, 2.00 equiv) and freshly degassed H₂O (1.5 mL) were added and the suspension was stirred at 80 °C for 16 h under N₂. After cooling to ambient temperature, EtOAc (10 mL) was added, the organic phase was separated, and the aqueous phase was extracted with EtOAc (3 × 10 mL). After drying of the combined organic phases over Na₂SO₄, the crude mixture was concentrated in vacuo. Purification by column chromatography (SiO₂, n-hexane/EtOAc = 4:1) afforded the desired product 3a (91.1 mg, 85%) as a colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 8.57 (d, J = 4.6 Hz, 1 H), 7.82 (dt, J = 7.8, 1.5 Hz, 1 H), 7.57 (dd, J = 3.9, 3.9 Hz, 1 H), 7.38–7.22 (m, 3 H), 7.19–7.09 (m, 2 H), 5.97 (d, J = 2.0 Hz, 1 H), 5.18 (d, J = 8.1 Hz, 1 H), 5.02 (d, J = 2.2 Hz, 1 H), 4.65 (q, J = 6.6 Hz, 1 H), 4.07 (td, J = 6.7, 1.3 Hz, 2 H), 3.96 (s, 2 H), 3.66 (d, J = 1.3 Hz, 3 H), 3.30 (d, J = 5.1 Hz, 2 H), 1.58 (q, J = 6.9 Hz, 2 H), 1.40 (s, 9 H), 1.35–1.27 (m, 2 H), 0.90 (t, J = 7.4 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 172.9 (C_q), 166.5 (C_q), 155.3 (C_q), 151.4 (C_q), 149.6 (CH), 138.4 (CH), 137.8 (C_q), 136.9 (C_q), 134.6 (C_q), 128.7 (C_q), 126.0 (C_q), 122.6 (CH), 122.2 (CH), 121.0 (CH), 120.8 (CH), 118.8 (CH), 110.7 (CH₂), 110.3 (CH), 79.8 (C_q), 64.8 (CH₂), 62.6 (CH₂), 54.1 (CH), 52.4 (CH₃), 30.7 (CH₂), 28.4 (CH₃), 27.0 (CH₂), 19.2 (CH₂), 13.8 (CH₃). HRMS (ESI): m/z [M + Na]⁺ calcd for C₃₀H₃₇N₃O₆Na: 558.2575; found: 558.2575.
68 Brals J, Smith JD, Ibrahim F, Gallou F, Handa S. ACS Catal. 2017; 7: 7245

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