Single-Electron-Transfer Oxidation of Trifluoroborates and Silicates with Organic Reagents: A Comparative Study

Ludwig Chenneberg; Christophe Lévêque; Vincent Corcé; Alexandre Baralle; Jean-Philippe Goddard; Cyril Ollivier; Louis Fensterbank

doi:10.1055/s-0035-1561337

Synlett, Inhaltsverzeichnis

Synlett 2016; 27(05): 731-735
DOI: 10.1055/s-0035-1561337

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Single-Electron-Transfer Oxidation of Trifluoroborates and Silicates with Organic Reagents: A Comparative Study

Ludwig Chenneberg

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

,

Christophe Lévêque

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

,

Vincent Corcé

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

,

Alexandre Baralle

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

,

Jean-Philippe Goddard*

^bLaboratoire de Chimie Organique et Bioorganique EA 4566, Université de Haute-Alsace, Ecole Nationale Supérieure de Chimie de Mulhouse, 3 Bis Rue Alfred Werner, 68093 Mulhouse Cedex, France eMail: jean-philippe.goddard@uha.fr

,

Cyril Ollivier*

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

,

Louis Fensterbank*

^aInstitut Parisien de Chimie Moléculaire, UMR CNRS 8232, Sorbonne Universités UPMC Univ Paris 06, 4 Place Jussieu, CC 229, 75252 Paris Cedex 05, France eMail: louis.fensterbank@upmc.fr eMail: cyril.ollivier@upmc.fr

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Abstract

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Abstract

In this report, the single-electron-transfer oxidation of alkyl trifluoroborates and silicates has been studied. Different types of oxidation reagents have been examined, focusing on organic oxidants and particularly the use of dyes in photocatalytic oxidations. Both trifluoroborates and silicates could provide C-centered radicals when using a tritylium salt or the Ledwith–Weitz aminium salt. Photocatalysis with the Fukuzumi reagent suggested that trifluoroborates are more easily oxidized than biscatecholato silicates under these conditions.

Key words

radicals - dyes - photocatalysis - trifluoroborates - silicates - single-electron transfer - oxidation

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Referenzen

References and Notes

1a Dalko PI. Tetrahedron 1995; 51: 7579
1b Jahn U. Radicals in Synthesis III. In Topics in Current Chemistry. Vol. 320. Heinrich M, Gansäuer A. Wiley-VCH; Weinheim: 2012: 121
1c Jahn U. Radicals in Synthesis III. In Topics in Current Chemistry. Vol. 320. Heinrich M, Gansäuer A. Wiley-VCH; Weinheim: 2012: 191
1d Jahn U. Radicals in Synthesis III. In Topics in Current Chemistry. Vol. 320. Heinrich M, Gansäuer A. Wiley-VCH; Weinheim: 2012: 323
1e Gansäuer A, Bluhm H. Chem. Rev. 2000; 100: 2771

2a Schuster GB. Pure Appl. Chem. 1990; 62: 1565
2b Shundrin LA, Bardin VV, Frohn H.-J. Z. Anorg. Allg. Chem. 2004; 630: 1253
2c Molander GA, Colombel V, Braz VA. Org. Lett. 2011; 13: 1852
2d Lockner JW, Dixon DD, Risgaard R, Baran PS. Org. Lett. 2011; 13: 5628
2e Fujiwara Y, Domingo V, Seiple IB, Gianatassio R, Bel MD, Baran PS. J. Am. Chem. Soc. 2011; 133: 3292
2f Liwosz TW, Chemler SR. Org. Lett. 2013; 15: 3034
2g Neufeldt SR, Seigerman CK, Sanford MS. Org. Lett. 2013; 15: 2302

For the oxidation of boronic acids, see

2h Brown HC, Hébert NC, Snyder CH. J. Am. Chem. Soc. 1961; 83: 1001
2i Demir AS, Reis Ö, Emrullahoglu M. J. Org. Chem. 2003; 68: 578
2j Dickschat A, Studer A. Org. Lett. 2010; 12: 3972
2k Tobisu M, Koh K, Furukawa T, Chatani N. Angew. Chem. Int. Ed. 2012; 51: 11363

3a Corcé V, Chamoreau LM, Derat E, Goddard J.-P, Ollivier C, Fensterbank L. Angew. Chem. Int. Ed. 2015; 54: 11414

During the course of our investigation, the following complementary report appeared, see:

3b Jouffroy M, Primer DN, Molander GA. J. Am. Chem. Soc. 2016; 138 in press; DOI: 10.1021/jacs.5b10963

4a Holmes RR. Chem. Rev. 1990; 90: 17
4b Chuit C, Corriu RJ. P, Reye C, Young JC. Chem. Rev. 1993; 93: 1371

5 Sorin G, Mallorquin RM, Contie Y, Baralle A, Malacria M, Goddard J-P, Fensterbank L. Angew. Chem. Int. Ed. 2010; 49: 8721

6a Nishigaichi Y, Orimi T, Takuwa A. J. Organomet. Chem. 2009; 694: 3837
6b Carzola C, Metay E, Andrioletti B, Lemaire M. Tetrahedron Lett. 2009; 50: 6855

7 For seminal work, see: Yoshida J.-I, Tamao K, Kakui T, Kurita A, Murata M, Yamada K, Kumada M. Organometallics 1982; 1: 369

Tritylium is known as a hydride abstractor, for a recent application, see:

8a Xie Z, Liu L, Chen W, Zheng H, Xu QH, Yuan H, Lou H. Angew. Chem. Int. Ed. 2014; 53: 3904 ; and references cited therein

It has been used as a sacrificial electron acceptor in photoredox catalysis, see:

8b Daniel M, Fensterbank L, Goddard J.-P, Ollivier C. Org. Chem. Front. 2014; 1: 551

9 To a Schlenk flask was added potassium 5-hexenyl-1-trifluoroborate (1d) or potassium [18-crown-6] bis(catecholato)-5-hexenyl-1-silicate (3d, 0.3 mmol, 1 equiv), the oxidizing agent (0.3 mmol, 1 equiv), and TEMPO (0.9 mmol, 141 mg, 3 equiv). The Schlenk flask was sealed with a rubber septum, and evacuated–purged with vacuum–argon three times. Degassed Et₂O or DMF (3 mL) was introduced followed by two freeze–pump–thaw cycles. The reaction mixture was stirred at room temperature for 24 h under an argon atmosphere. The reaction mixture was diluted with Et₂O (50 mL), washed with H₂O or NaHCO_3- (2×), brine (2×), dried over MgSO₄, and evaporated under reduced pressure. The reaction residue was purified by flash column chromatography on silica gel to afford an inseparable mixture of 4d and 4d′ in a 9:1 to 10:1 ratio and an overall yield (37–61%) depending on the oxidizing agent. Compound 4d: ¹H NMR (400 MHz, CDCl₃): δ = 5.82 (m, 1 H), 5.01 (m, 1 H), 4.94 (m, 1 H), 3.73 (t, J = 6.1 Hz, 2 H), 2.07 (q, J = 7.2 Hz, 2 H), 1.55–1.20 (m, 10 H), 1.14 (s, 6 H), 1.09 (s, 6 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 139.1, 114.5, 80.8, 59.9, 59.8, 39.7, 34.0, 33.2, 28.4, 25.9, 20.3, 17.3 ppm. Compound 4d′: ¹H NMR (400 MHz, CDCl₃): characteristic signal at δ = 3.64 ppm (CH ₂O). ¹³C NMR (100 MHz, CDCl₃): characteristic signal at δ = 76.7 ppm (CH₂O).

10a Herath AC, Becker JY. J. Electroanal. Chem. 2008; 619-620: 98
10b Brinkhaus KH. G, Steckhan E, Schmidt W. Acta Chem. Scand., Ser. B 1983; 37: 499
10c Wend R, Steckhan E. Electrochim. Acta 1983; 42: 2027

For a recent use, see:

10d Drew SL, Lawrence AL, Sherburn MS. Angew. Chem. Int. Ed. 2013; 52: 4221

(e) For a review, see: Jia, X. Synthesis 2016, 48, 18.

11 In comparison, oxidation with 1 equiv of Cu(OAc)₂ gave 45% yield of 4a and with 1 equiv of DMP, 26% of 4a.

For selected reviews on visible-light photoredox catalysis, see:

12a Zeitler K. Angew. Chem. Int. Ed. 2009; 48: 9785
12b Yoon TP, Ischay MA, Du J. Nat. Chem. 2010; 2: 527
12c Teplý F. Collect. Czech. Chem. Commun. 2011; 76: 859
12d Narayanaman JM. R, Stephenson CR. J. Chem. Soc. Rev. 2011; 40: 102
12e Tucker JW, Stephenson CR. J. J. Org. Chem. 2012; 77: 1617
12f Xuan J, Xiao W.-J. Angew. Chem. Int. Ed. 2012; 51: 6828
12g Ischay MA, Yoon TP. Eur. J. Org. Chem. 2012; 3359
12h Maity S, Zheng N. Synlett 2012; 23: 1851
12i Shi L, Xia W. Chem. Soc. Rev. 2012; 41: 7687
12j Xi Y, Yi H, Lei A. Org. Biomol. Chem. 2013; 11: 2387
12k Prier CK, Rankic DA, MacMillan DW. C. Chem. Rev. 2013; 113: 5322
12l Hari DP, König B. Angew. Chem. Int. Ed. 2013; 52: 4734
12m Reckenthäler M, Griesbeck AG. Adv. Synth. Catal. 2013; 355: 2727
12n Koike T, Akita M. Synlett 2013; 24: 2492
12o Xuan J, Lu L.-Q, Chen J.-R, Xiao W.-J. Eur. J. Org. Chem. 2013; 6755
12p Zou Y.-Q, Chen J.-R, Xiao W.-J. Angew. Chem. Int. Ed. 2013; 52: 11701
12q Hu J, Wang J, Nguyen TH, Zheng N. Beilstein J. Org. Chem. 2013; 9: 1977
12r Xie J, Jin H, Xu P, Zhu C. Tetrahedron Lett. 2014; 55: 36
12s Koike T, Akita M. Inorg. Chem. Front. 2014; 1: 562
12t Hopkinson MN, Sahoo B, Li J.-L, Glorius F. Chem. Eur. J. 2014; 20: 3874
12u Schultz DM, Yoon TP. Science 2014; 343: 985

For recent books, see:

12v Chemical Photocatalysis. König B. DeGruyter; Berlin: 2013
12w Photochemically Generated Intermediates in Synthesis. Albini A, Fagnoni M. John Wiley and Sons; Hoboken: 2013

13a Yasu Y, Koike T, Akita M. Adv. Synth. Catal. 2012; 354: 3414
13b Miyazawa K, Yasu Y, Koike T, Akita M. Chem. Commun. 2013; 49: 7249
13c Koike T, Akita M. Synlett 2013; 24: 2492
13d Miyazawa K, Koike T, Akita M. Adv. Synth. Catal. 2014; 356: 2749
13e Li Y, Miyazawa K, Koike T, Akita M. Org. Chem. Front. 2015; 2: 319
13f Huang H, Zhang G, Gong L, Zhang S, Chen Y. J. Am. Chem. Soc. 2014; 136: 2280
13g Tellis JC, Primer DN, Molander GA. Science 2014; 345: 433
13h Primer DN, Karakaya I, Tellis JC, Molander GA. J. Am. Chem. Soc. 2015; 137: 2195
13i Gutierrez O, Tellis JC, Primer DN, Molander GA, Kozlowski MC. J. Am. Chem. Soc. 2015; 137: 4896
13j Karakaya I, Primer DN, Molander GA. Org. Lett. 2015; 17: 3294
13k Yamashita Y, Tellis JC, Molander GA. Proc. Natl. Acad. Sci. U.S.A. 2015; 112: 12026
13l Huang H, Jia K, Chen Y. Angew. Chem. Int. Ed. 2015; 54: 1881

14 Allyl-, cyclopentyl-, t-BuSiF₅K₂ did not give any TEMPO adduct 4 in the following conditions {2 mol% Ir[(dF(CF₃)ppy)₂(bpy)](PF₆), acetone or DMF, TEMPO (2.5 equiv), blue LED}.

15a Fukuzumi S, Ohkubo K. Org. Biomol. Chem. 2014; 12: 6059
15b Nicewicz DA, Nguyen TM. ACS Catal. 2014; 4: 355
15c Ravelli D, Fagnoni M. ChemCatChem 2012; 4: 169

For a recent use, see:

15d Griffin JD, Zeller MA, Nicewicz DA. J. Am. Chem. Soc. 2015; 137: 11340

16 Zhang X.-F, Zhang I, Liu L. Photochem. Photobiol. 2010; 86: 492

17a Fukuzumi S, Kotani H, Okhubo K, Ogo S, Tkachenko NV, Lemmetyinen H. J. Am. Chem. Soc. 2004; 126: 1600
17b Benniston AC, Harriman A, Li P, Rostron JP, van Ramesdonk HJ, Groeneveld MM, Zhang H, Verhoeven JW. J. Am. Chem. Soc. 2005; 127: 16054

18 To a Schlenk flask were added the organotrifluoroborate 1 or organosilicate 3 (0.3 mmol, 1 equiv), 9-mesityl-10-methylacridinium perchlorate as photocatalyst (0.03 mmol, 10 mol%), and TEMPO (0.66 mmol, 2.2 equiv.). The Schlenk flask was sealed with a rubber septum and evacuated–purged with vacuum–argon three times. Degassed DMF (3 mL) was introduced followed by two freeze–pump–thaw cycles. The reaction mixture was stirred under blue LEDs irradiation at room temperature for 24 h under an argon atmosphere. The reaction mixture was diluted with Et₂O (50 mL), washed with sat. NaHCO₃ (2×), brine (2×), dried over MgSO₄, and evaporated under reduced pressure. The reaction residue was purified by flash column chromatography on silica gel.
19 The generated TEMPO N-oxide anion could be silylated or borylated. The resulting anionic products would be eliminated during the aqueous workup. We thank one of the referees for this suggestion.

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