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

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook X Linkedin Weibo

Download PDF

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

cluster

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

› Author AffiliationsGenerous support from the Deutsches Zentrum für Herz-Kreislaufforschung (DZHK) (PI at the German Centre for Cardiovascular Research), the European Research Council (ERC) (Advanced Grant 101021358), and the DFG (Gottfried-Wilhelm-Leibniz Prize) to L.A. are gratefully acknowledged. We are also grateful for support from the European Union’s Horizon 2020 research and innovation program, H2020 Marie Skłodowska-Curie Actions (Grant Agreement No. 860762) to T.O., and warmly acknowledge Novartis for financial support.

› Further Information

Abstract
Full Text
References
Supplementary Material

Buy Article Permissions and Reprints All articles of this category

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

Supporting Information

Supporting Information

Publication History

Received: 21 January 2024

Accepted after revision: 14 February 2024

Accepted Manuscript online:
14 February 2024

Article published online:
27 February 2024

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

References and Notes
1 Lau JL, Dunn MK. Bioorg. Med. Chem. 2018; 26: 2700

Crossref PubMed Search in Google Scholar
2 Fosgerau K, Hoffmann T. Drug Discovery Today 2015; 20: 122

Crossref PubMed Search in Google Scholar
3 Guillemard L, Kaplaneris N, Ackermann L, Johansson MJ. Nat. Rev. Chem. 2021; 5: 522

Crossref PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
5 Blaskovich MA. T. J. Med. Chem. 2016; 59: 10807

Crossref PubMed Search in Google Scholar
6 Bottecchia C, Noël T. Chem. Eur. J. 2019; 25: 26

Crossref PubMed Search in Google Scholar
7 Brandhofer T, García Mancheño O. Eur. J. Org. Chem. 2018; 6050

Crossref
8 Lee HG, Lautrette G, Pentelute BL, Buchwald SL. Angew. Chem. Int. Ed. 2017; 56: 3177

Crossref PubMed Search in Google Scholar
9 Vinogradova EV, Zhang C, Spokoyny AM, Pentelute BL, Buchwald SL. Nature 2015; 526: 687

Crossref PubMed Search in Google Scholar
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

Crossref Search in Google Scholar
11 Gensch T, James MJ, Dalton T, Glorius F. Angew. Chem. Int. Ed. 2018; 57: 2296

Crossref PubMed Search in Google Scholar
12 Chu JC. K, Rovis T. Angew. Chem. Int. Ed. 2018; 57: 62

Crossref PubMed Search in Google Scholar
13 Lapointe D, Fagnou K. Chem. Lett. 2010; 39: 1118

Crossref PubMed Search in Google Scholar
14 Wang W, Lorion MM, Shah J, Kapdi AR, Ackermann L. Angew. Chem. Int. Ed. 2018; 57: 14700

Crossref PubMed Search in Google Scholar
15 Mendive-Tapia L, Preciado S, García J, Ramón R, Kielland N, Albericio F, Lavilla R. Nat. Commun. 2015; 6: 7160

Crossref PubMed Search in Google Scholar
16 Ruiz-Rodríguez J, Albericio F, Lavilla R. Chem. Eur. J. 2010; 16: 1124

Crossref PubMed Search in Google Scholar
17 Hou X, Kaplaneris N, Yuan B, Frey J, Ohyama T, Messinis AM, Ackermann L. Chem. Sci. 2022; 13: 3461

Crossref PubMed Search in Google Scholar
18 Schischko A, Kaplaneris N, Rogge T, Sirvinskaite G, Son J, Ackermann L. Nat. Commun. 2019; 10: 3553

Crossref PubMed Search in Google Scholar
19 Schischko A, Ren H, Kaplaneris N, Ackermann L. Angew. Chem. Int. Ed. 2017; 56: 1576

Crossref PubMed Search in Google Scholar
20 Li B, Li X, Han B, Chen Z, Zhang X, He G, Chen G. J. Am. Chem. Soc. 2019; 141: 9401

Crossref PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
22 Yin X.-S, Qi W.-Y, Shi B.-F. Chem. Sci. 2021; 12: 13137

Crossref PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
25 Liu T, Qiao JX, Poss MA, Yu J.-Q. Angew. Chem. Int. Ed. 2017; 56: 10924

Crossref PubMed Search in Google Scholar
26 Bai Z, Cai C, Yu Z, Wang H. Angew. Chem. Int. Ed. 2018; 57: 13912

Crossref PubMed Search in Google Scholar
27 Tran LD, Daugulis O. Angew. Chem. Int. Ed. 2012; 51: 5188

Crossref PubMed Search in Google Scholar
28 Reddy BV. S, Reddy LR, Corey EJ. Org. Lett. 2006; 8: 3391

Crossref PubMed Search in Google Scholar
29 Gandeepan P, Müller T, Zell D, Cera G, Warratz S, Ackermann L. Chem. Rev. 2019; 119: 2192

Crossref PubMed Search in Google Scholar
30 Hu Y, Zhou B, Wang C. Acc. Chem. Res. 2018; 51: 816

Crossref PubMed Search in Google Scholar
31 Ruan Z, Sauermann N, Manoni E, Ackermann L. Angew. Chem. Int. Ed. 2017; 56: 3172

Crossref PubMed Search in Google Scholar
32 Jei BB, Yang L, Ackermann L. Chem. Eur. J. 2022; 28: e202200811

Crossref PubMed Search in Google Scholar
33 Kaplaneris N, Kaltenhäuser F, Sirvinskaite G, Fan S, De Oliveira T, Conradi L.-C, Ackermann L. Sci. Adv. 2021; 7: eabe6202

Crossref PubMed Search in Google Scholar
34 Kaplaneris N, Son J, Mendive-Tapia L, Kopp A, Barth ND, Maksso I, Vendrell M, Ackermann L. Nat. Commun. 2021; 12: 3389

Crossref PubMed Search in Google Scholar
35 Luo Z, Whitcomb CA, Kaylor N, Zhang Y, Zhang S, Davis RJ, Gunnoe TB. ChemCatChem 2021; 13: 260

Crossref Search in Google Scholar
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

Crossref Search in Google Scholar
37 Kaplaneris N, Rogge T, Yin R, Wang H, Sirvinskaite G, Ackermann L. Angew. Chem. Int. Ed. 2019; 58: 3476

Crossref PubMed Search in Google Scholar
38 Wang W, Subramanian P, Martinazzoli O, Wu J, Ackermann L. Chem. Eur. J. 2019; 25: 10585

Crossref PubMed Search in Google Scholar
39 Prat D, Hayler J, Wells A. Green Chem. 2014; 16: 4546

Crossref Search in Google Scholar
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

Crossref Search in Google Scholar
41 Cortes-Clerget M, Yu J, Kincaid JR. A, Walde P, Gallou F, Lipshutz BH. Chem. Sci. 2021; 12: 4237

Crossref PubMed Search in Google Scholar
42 Hauk P, Wencel-Delord J, Ackermann L, Walde P, Gallou F. Curr. Opin. Colloid Interface Sci. 2021; 56: 101506

Crossref Search in Google Scholar
43 Gallou F. Chimia 2020; 74: 538

Crossref PubMed Search in Google Scholar
44 Steven A. Synthesis 2019; 51: 2632

Thieme Connect Search in Google Scholar
45 Anastas P, Eghbali N. Chem. Soc. Rev. 2010; 39: 301

Crossref PubMed Search in Google Scholar
46 Anastas PT, Kirchhoff MM. Acc. Chem. Res. 2002; 35: 686

Crossref PubMed Search in Google Scholar
47 Lipshutz BH, Ghorai S. Aldrichimica Acta 2012; 45: 3

PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
49 Cortes-Clerget M, Lee NR, Lipshutz BH. Nat. Protoc. 2019; 14: 1108

Crossref PubMed Search in Google Scholar
50 Borrego E, Caballero A, Pérez PJ. Organometallics 2022; 41: 3084

Crossref PubMed Search in Google Scholar
51 Sarathkumar S, Kavala V, Yao C.-F. Org. Lett. 2021; 23: 1960

Crossref PubMed Search in Google Scholar
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

Crossref PubMed Search in Google Scholar
53 Mandal A, Garai B, Dana S, Bera R, Baidya M. Chem. Asian J. 2020; 15: 4009

Crossref PubMed Search in Google Scholar
54 Nie R, Lai R, Lv S, Xu Y, Guo L, Wang Q, Wu Y. Chem. Commun. 2019; 55: 11418

Crossref PubMed Search in Google Scholar
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

Crossref Search in Google Scholar
56 Drev M, Grošelj U, Ledinek B, Perdih F, Svete J, Štefane B, Požgan F. Org. Lett. 2018; 20: 5268

Crossref PubMed Search in Google Scholar
57 Wu S, Wu X, Fu C, Ma S. Org. Lett. 2018; 20: 2831

Crossref PubMed Search in Google Scholar
58 Ali MA, Yao X, Sun H, Lu H. Org. Lett. 2015; 17: 1513

Crossref PubMed Search in Google Scholar
59 Ackermann L, Pospech J. Org. Lett. 2011; 13: 4153

Crossref PubMed Search in Google Scholar
60 Ackermann L. Org. Lett. 2005; 7: 3123

Crossref PubMed Search in Google Scholar
61 Dhawa U, Kaplaneris N, Ackermann L. Org. Chem. Front. 2021; 8: 4886

Crossref Search in Google Scholar
62 Kaplaneris N, Vilches-Herrera M, Wu J, Ackermann L. ACS Sustainable Chem. Eng. 2022; 10: 6871

Crossref Search in Google Scholar
63 Wei D, Lin G.-Q. Chin. J. Chem. 2024; 42: 533

Crossref Search in Google Scholar
64 Ackermann L. Acc. Chem. Res. 2020; 53: 84

Crossref PubMed Search in Google Scholar
65 Loup J, Dhawa U, Pesciaioli F, Wencel-Delord J, Ackermann L. Angew. Chem. Int. Ed. 2019; 58: 12803

Crossref PubMed Search in Google Scholar
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

Crossref Search in Google Scholar
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

Crossref Search in Google Scholar

Subscribe to RSS

Share / Bookmark

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

Abstract

Key words

Supporting Information

Publication History

References and Notes