Martin Silicates as Versatile Radical Precursors in Photoredox/ Nickel Dual Catalysis

Maxim-Aleksa Wiethoff; Mehdi Abdellaoui; Thomas Deis; Vincent Corcé; Gilles Lemière; Cyril Ollivier; Louis Fensterbank

doi:10.1055/a-2059-3498

Synlett, Table of Contents

Synlett 2023; 34(12): 1467-1471
DOI: 10.1055/a-2059-3498

cluster

Special Issue Honoring Masahiro Murakami’s Contributions to Science

Martin Silicates as Versatile Radical Precursors in Photoredox/ Nickel Dual Catalysis

Authors

Maxim-Aleksa Wiethoff‡

^aWestfälische Wilhelms-Universität Münster, Organisch-Chemisches Institut, Corrensstraße 40, 48149 Münster, Germany
Mehdi Abdellaoui‡

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France
Thomas Deis

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France
Vincent Corcé

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France
Gilles Lemière∗

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France
Cyril Ollivier∗

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France
Louis Fensterbank ∗

^bSorbonne Université, CNRS, Institut Parisien de Chimie Moléculaire, 4 Place Jussieu, C 229, 75252 Paris, Cedex 05, France

Abstract

All articles of this category

Abstract

A cross-coupling methodology is described based on the nickel-catalyzed connection of an aryl moiety to an alkyl radical generated by photoinduced single-electron oxidation of a silicate formed from a Martin spirosilane. Complementary to the other anionic radical precursors in photoredox catalysis, Martin silicates permit access to highly reactive alkyl radicals directly engageable in smooth C(sp²)–C(sp³) bond-formation reactions.

Key words

dual catalysis - photoredox catalysis - nickel catalysis - cross-coupling - Martin silicates - C–C bond formation

Full Text

References

References and Notes
1 Chan AY, Perry IB, Bissonnette NB, Buksh BF, Edwards GA, Frye LI, Garry OL, Lavagnino MN, Li BX, Liang Y, Mao E, Millet A, Oakley JV, Reed NL, Sakai HA, Seath CP, MacMillan DW. C. Chem. Rev. 2022; 122: 1485
2 Crespi S, Fagnoni M. Chem. Rev. 2020; 120: 9790
3 Corcé V, Ollivier C, Fensterbank L. Chem. Soc. Rev. 2022; 51: 1470
4 Zuo Z, Ahneman DT, Chu L, Terrett JA, Doyle AG, MacMillan DW. C. Science 2014; 345: 437
5 Tellis JC, Primer DN, Molander GA. Science 2014; 345: 433
6 Knauber T, Chandrasekaran R, Tucker JW, Chen JM, Reese M, Rankic DA, Sach N, Helal C. Org. Lett. 2017; 19: 6566
7 Nakajima K, Nojima S, Nishibayashi Y. Angew. Chem. Int. Ed. 2016; 55: 14106
8 Basch CH, Liao J, Xu J, Piane JJ, Watson MP. J. Am. Chem. Soc. 2017; 139: 5313
9 Klauck FJ. R, James MJ, Glorius F. Angew. Chem. Int. Ed. 2017; 56: 12336
10 Huang L, Ji T, Rueping M. J. Am. Chem. Soc. 2020; 142: 3532

11a Le C, Liang YF, Evans RW, Li XM, MacMillan DW. C. Nature 2017; 547: 79
11b Perry IB, Brewer TF, Sarver PJ, Schultz DM, DiRocco DA, MacMillan DW. C. Nature 2018; 560: 70
11c Shaw MH, Shurtleff VW, Terrett JA, Cuthbertson JD, MacMillan DW. C. Science 2016; 352: 1304

12a Corcé V, Chamoreau L.-M, Derat E, Goddard J.-P, Ollivier C, Fensterbank L. Angew. Chem. Int. Ed. 2015; 54: 11414
12b Lemière G, Millanvois A, Ollivier C, Fensterbank L. Chem. Rec. 2021; 21: 1119

13 Lévêque C, Chenneberg L, Corcé V, Goddard J.-P, Ollivier C, Fensterbank L. Org. Chem. Front. 2016; 3: 462
14 Jouffroy M, Primer DN, Molander GA. J. Am. Chem. Soc. 2016; 138: 475
15 Ikarashi G, Morofuji T, Kano N. Chem. Commun. 2020; 56: 10006
16 Morofuji T, Matsui Y, Ohno M, Ikarashi G, Kano N. Chem. Eur. J. 2021; 27: 6713
17 Joshi-Pangu A, Lévesque F, Roth HG, Oliver SF, Campeau L.-C, Nicewicz D, DiRocco DA. J. Org. Chem. 2016; 81: 7244
18 White AR, Wang L, Nicewicz DA. Synlett 2019; 30: 827
19 Fukuzumi S, Kotani H, Ohkubo K, Ogo S, Tkachenko NV, Lemmetyinen H. J. Am. Chem. Soc. 2004; 126: 1600
20 Uygur M, Danelzik T, Garcia-Mancheño O. Chem. Commun. 2019; 55: 2980
21 Cross-Coupling Reaction; General Procedure A flame-dried, sealed, microwave tube, purged by three argon/vacuum cycles, was charged with the appropriate silicate 1a–h (0.2 mmol, 1 equiv), NiBr₂BPhen (5.5 mg, 0.01 mmol, 5 mol%), and photocatalyst PC1 (5.7 mg, 0.01 mmol, 5 mol%) under argon, along with the appropriate aryl bromide or iodide (0.4 mmol, 2 equiv), if solid. (When the aryl bromide was a liquid, it was introduced from a microsyringe after adding the solvent under argon.) Distilled CH₂Cl₂ was then added (0.2 M) under argon, followed by three freeze–pump–thaw cycles to degas the mixture. The mixture was then irradiated with a blue LED for 24 h at r.t. The reaction was then quenched with sat. aq K₂CO₃ (10 mL) and the mixture was extracted with Et₂O (3 × 20 mL) and H₂O (3 × 20 mL). The combined organic layers were concentrated under vacuum, and the crude product was purified by flash chromatography (silica gel). 1-[4-(Tetrahydro-2H-pyran-4-yl)phenyl]-1H-pyrrole (4) Brown solid; yield: 19.2 mg (51%); mp 119.8–124.1 °C. ¹H NMR: (300 MHz, CDCl₃): δ = 7.40–7.34 (m, 2 H), 7.33–7.27 (m, 2 H), 7.09 (t, J = 2.2 Hz, 2 H), 6.37 (t, J = 2.2 Hz, 2 H), 4.19–4.07 (m, 2 H), 3.58 (dt, J = 11.3, 3.1 Hz, 2 H), 2.81 (tt, J = 10.6, 5.5 Hz, 1 H), 1.96–1.75 (m, 4 H). ¹³C NMR: (75 MHz, CDCl₃): δ = 143.5, 139.3, 127.9, 120.9, 119.5, 110.4, 68.5, 41.2, 34.1. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₅H₁₈NO: 228.1383; found: 228.1384. Methyl 6-(Tetrahydro-2H-pyran-4-yl)-2-naphthoate (11) White solid; yield: 37.9 mg (70%); mp 115.1–119.1 °C. ¹H NMR: (400 MHz, CDCl₃): δ = 8.58 (s, 1 H), 8.05 (dd, J = 8.6, 1.7 Hz, 1 H), 7.91 (d, J = 8.5 Hz, 1 H), 7.83 (d, J = 8.6 Hz, 1 H), 7.68 (d, J = 1.7 Hz, 1 H), 7.44 (dd, J = 8.5, 1.8 Hz, 1 H), 4.13 (ddt, J = 11.5, 4.3, 1.6 Hz, 2 H), 3.98 (s, 3 H), 3.59 (td, J = 11.6, 2.5 Hz, 2 H), 2.95 (tt, J = 11.6, 4.2 Hz, 1 H), 2.06–1.78 (m, 4 H). ¹³C NMR: (101 MHz, CDCl₃): δ = 167.3, 146.0, 135.8, 131.3, 130.8, 129.5, 127.8, 126.9, 126.5, 125.4, 124.6, 68.3, 52.2, 41.8, 33.7. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₇H₁₉O: 271.1329; found: 271.1327. tert-Butyl 4-(Tetrahydro-2H-pyran-4-ylmethylene)piperidine-1-carboxylate (21)Brown solid; yield: 27.0 mg (48%); mp 97–100.5 °C. ¹H NMR: (300 MHz, CDCl₃): δ = 5.06 (d, J = 8.5 Hz, 1 H), 3.99–3.87 (m, 2 H), 3.50–3.32 (m, 6 H), 2.55–2.33 (m, 1 H), 2.16 (dt, J = 31.4, 5.7 Hz, 4 H), 1.42 (s, 13 H). ¹³C NMR: (75 MHz, CDCl₃): δ = 154.9, 134.8, 128.8, 79.6, 67.8, 35.9, 33.5, 33.4, 28.8, 28.6. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₂₈NO₃: 282.2064; found: 282.2068. Methyl 6-sec-Butyl-2-naphthoate (24) Yellow oil; yield: 19.7 mg (41%). ¹H NMR: (400 MHz, CDCl₃): δ = 8.57 (d, J = 1.8 Hz, 1 H), 8.03 (dd, J = 8.6, 1.7 Hz, 1 H), 7.85 (dd, J = 27.2, 8.6 Hz, 2 H), 7.64 (d, J = 1.8 Hz, 1 H), 7.41 (dd, J = 8.5, 1.8 Hz, 1 H), 3.98 (s, 3 H), 2.86–2.73 (m, 1 H), 1.78–1.63 (m, 2 H), 1.33 (d, J = 6.9 Hz, 3 H), 0.86 (t, J = 7.4 Hz, 3 H). ¹³C NMR: (101 MHz, CDCl₃): δ = 167.6, 148.1, 136.0, 129.5, 127.9, 126.9, 125.4, 125.3, 52.3, 42.1, 31.1, 21.8, 12.4. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₆H₁₉O₂: 243.1380; found: 243.1376.
22 For the introduction of a methyl group and its ¹³C- and ²H-labeled analogues, see: Abdellaoui M, Deis T, Wiethoff M.-A, Bahri C, Lemière G, Ollivier C, Fensterbank L. Adv. Synth. Catal. 2023; 365: 884

Supplementary Material

Supporting Information (PDF) (opens in new window)