Catalytic Si/B Exchange Condensation: A Green B–C Coupling Method That Provides Access to Monodisperse (Het)arylborane ‘Trimers’

The potential of our metal-free B–C coupling method using catalytic Si/B exchange condensation is demonstrated by the synthesis of a series of monodisperse (het)arylborane oligomers with four (het)arene moieties and three boron centers (i.e., ‘trimers’). Photophysical and electrochemical investigations evidenced effective π-conjugation over the (het)arene rings and the boron centers.

Key words

boron - B–C bond formation - furan - thiophene - organocatalysis - organoboranes - monodisperse oligomers - conjugated materials

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References

References
1 These authors contributed equally to this work.

Reviews:

2a Wade CR, Broomsgrove AE. J, Aldridge S, Gabbai FP. Chem. Rev. 2010; 110: 3958
2b Jäkle F. Chem. Rev. 2010; 110: 3985
2c Hudson ZM, Wang S. Dalton Trans. 2011; 7805
2d Tanaka K, Chujo Y. Macromol. Rapid Commun. 2012; 33: 1235
2e Zhao H, Leamer LA, Gabbai FP. Dalton Trans. 2013; 8164
2f He X, Baumgartner T. RSC Adv. 2013; 3: 11334
2g Wakamiya A, Yamaguchi S. Bull. Chem. Soc. Jpn. 2015; 88: 1357
2h Ji L, Griesbeck S, Marder TB. Chem. Sci. 2017; 8: 846
2i Helten H. In Encyclopedia of Inorganic and Bioinorganic Chemistry . Scott RA. Wiley; Chichester: 2017. DOI: https://doi.org/ 10.1002/9781119951438.eibc2496

Selected examples:

3a Wakamiya A, Mishima K, Ekawa K, Yamaguchi S. Chem. Commun. 2008; 579
3b Kim Y, Huh H.-S, Lee MH, Lenov IL, Zhao H, Gabbaï FP. Chem. Eur. J. 2011; 17: 2057
3c Marwitz AJ. V, Lamm AN, Zakharov LN, Vasiliu M, Dixon DA, Liu S.-Y. Chem. Sci. 2012; 3: 825
3d Levine DR, Caruso A, Siegler MA, Tovar JD. Chem. Commun. 2012; 6256
3e Neue B, Araneda JF, Piers WE, Parvez M. Angew. Chem. Int. Ed. 2013; 52: 9966
3f Hirai H, Nakajima K, Nakatsuka S, Shiren K, Ni J, Nomura S, Ikuta T, Hatakeyama T. Angew. Chem. Int. Ed. 2015; 54: 13581
3g Hertz VM, Bolte M, Lerner H.-W, Wagner M. Angew. Chem. Int. Ed. 2015; 54: 8800
3h Krieg M, Reicherter F, Haiss P, Ströbele M, Eichele K, Treanor M.-J, Schaub R, Bettinger HF. Angew. Chem. Int. Ed. 2015; 54: 8284
3i Ji L, Edkins RM, Lorbach A, Krummenacher I, Bruckner C, Eichhorn A, Braunschweig H, Engels B, Low PJ, Marder TB. J. Am. Chem. Soc. 2015; 137: 6750
3j Wang X.-Y, Narita A, Feng X, Müllen K. J. Am. Chem. Soc. 2015; 137: 7668
3k Wang S, Yang D.-T, Lu J, Shimogawa H, Gong S, Wang X, Mellerup SK, Wakamiya A, Chang Y.-L, Yang C, Lu ZH. Angew. Chem. Int. Ed. 2015; 54: 15074
3l Osumi S, Saito S, Dou C, Matsuo K, Kume K, Yoshikawa H, Awaga K, Yamaguchi S. Chem. Sci. 2016; 7: 219
3m Matsuo K, Saito S, Yamaguchi S. Angew. Chem. Int. Ed. 2016; 55: 11984
3n Crossley DL, Kahan RJ, Endres S, Warner AJ, Smith RA, Cid J, Dunsford JJ, Jones JE, Vitorica-Yrezabal I, Ingleson MJ. Chem. Sci. 2017; 8: 7969
3o Schickedanz K, Radtke J, Bolte M, Lerner H.-W, Wagner M. J. Am. Chem. Soc. 2017; 139: 2842
3p John A, Bolte M, Lerner H.-W, Wagner M. Angew. Chem. Int. Ed. 2017; 56: 5588

4 Ren Y, Jäkle F. Dalton Trans. 2016; 13996

For examples of thiophene–borane-based materials, see:

5a Wakamiya A, Mori K, Araki T, Yamaguchi S. J. Am. Chem. Soc. 2009; 131: 10850
5b Iida A, Yamaguchi S. J. Am. Chem. Soc. 2011; 133: 6952
5c Poon C.-T, Lam WH, Yam VW.-W. J. Am. Chem. Soc. 2011; 133: 19622
5d Braunschweig H, Damme A, Jimenez-Halla JO. C, Hörl C, Krummenacher I, Kupfer T, Mailänder L, Radacki K. J. Am. Chem. Soc. 2012; 134: 20169
5e Braunschweig H, Dyakonov V, Engels B, Falk Z, Hörl C, Klein JH, Kramer T, Kraus H, Krummenacher I, Lambert C, Walter C. Angew. Chem. Int. Ed. 2013; 52: 12852
5f Mercier LG, Piers WE, Harrington RW, Clegg W. Organometallics 2013; 32: 6820
5g Levine DR, Siegler MA, Tovar JD. J. Am. Chem. Soc. 2014; 136: 7132
5h Wang X.-Y, Zhuang F.-D, Wang R.-B, Wang X.-C, Cao X.-Y, Wang J.-Y, Pei J. J. Am. Chem. Soc. 2014; 136: 3764
5i Zhang Z, Edkins RM, Nitsch J, Fucke K, Eichhorn A, Steffen A, Wang Y, Marder TB. Chem. Eur. J. 2015; 21: 177
5j Sarkar SK, Kumar GR, Thilagar P. Chem. Commun. 2016; 4175
5k Shimogawa H, Yoshikawa O, Aramaki Y, Murata M, Wakamiya A, Murata Y. Chem. Eur. J. 2017; 23: 3784
5l Adachi Y, Ohshita J. Organometallics 2018; 37: 869

For furan–borane-based materials, see:

6a Wrackmeyer B, Nöth H. Chem. Ber. 1976; 109: 1075
6b Köhler T, Faderl J, Pritzkow H, Siebert W. Eur. J. Inorg. Chem. 2002; 2942
6c Braunschweig H, Dewhurst RD, Hörl C, Phukan AK, Pinzner F, Ullrich S. Angew. Chem. Int. Ed. 2014; 53: 3241
6d Braunschweig H, Dewhurst RD, Kramer T. Inorg. Chem. 2015; 54: 3619
6e Chen B, Nie H, Hu R, Qin A, Zhao Z, Tang B.-Z. Sci. China Chem. 2016; 59: 699

7a Matsumi N, Naka K, Chujo Y. J. Am. Chem. Soc. 1998; 120: 10776
7b Heilmann JB, Scheibitz M, Qin Y, Sundararaman A, Jäkle F, Kretz T, Bolte M, Lerner H.-W, Holthausen MC, Wagner M. Angew. Chem. Int. Ed. 2006; 45: 920
7c Nagai A, Murakami T, Nagata Y, Kokado K, Chujo Y. Macromolecules 2009; 42: 7217
7d Lorbach A, Bolte M, Li H, Lerner H.-W, Holthausen MC, Jäkle F, Wagner M. Angew. Chem. Int. Ed. 2009; 48: 4584

8a Yamaguchi I, Tominaga T, Sato M. Polym. Int. 2009; 58: 17
8b Reus C, Guo F, John A, Winhold M, Lerner H.-W, Jäkle F, Wagner M. Macromolecules 2014; 47: 3727
8c Wang X.-Y, Zhuang F.-D, Wang J.-Y, Pei J. Chem. Commun. 2015; 17532
8d Yin X, Guo F, Lalancette RA, Jäkle F. Macromolecules 2016; 49: 537
8e Yin X, Liu K, Ren Y, Lalancette RA, Loo Y.-L, Jäkle F. Chem. Sci. 2017; 8: 5497
8f Adachi Y, Ooyama Y, Ren Y, Yin X, Jäkle F, Ohshita J. Polym. Chem. 2018; 9: 291
8g Meng B, Ren Y, Liu J, Jäkle F, Wang L. Angew. Chem. Int. Ed. 2018; 57: 2183

9a Zhao W, Zhuang X, Wu D, Zhang F, Gehrig D, Laquai F, Feng X. J. Mater. Chem. A 2013; 1: 13878
9b Yin X, Chen J, Lalancette RA, Marder TB, Jäkle F. Angew. Chem. Int. Ed. 2014; 53: 9761
9c Baggett AW, Guo F, Li B, Liu S.-Y, Jäkle F. Angew. Chem. Int. Ed. 2015; 54: 11191

10a Bonifácio VD. B, Morgado J, Scherf U. J. Polym. Sci., Part A: Polym. Chem. 2008; 46: 2878
10b Adams IA, Rupar PA. Macromol. Rapid Commun. 2015; 36: 1336

11a Sundararaman A, Victor M, Varughese R, Jäkle F. J. Am. Chem. Soc. 2005; 127: 13748
11b Li H, Jäkle F. Angew. Chem. Int. Ed. 2009; 48: 2313
11c Chai J, Wang C, Jia L, Pang Y, Graham M, Cheng SZ. D. Synth. Met. 2009; 159: 1443
11d Li H, Jäkle F. Macromol. Rapid Commun. 2010; 31: 915
11e Chen P, Lalancette RA, Jäkle F. J. Am. Chem. Soc. 2011; 133: 8802

12a Lik A, Fritze L, Müller L, Helten H. J. Am. Chem. Soc. 2017; 139: 5692
12b Lik A, Jenthra S, Fritze L, Müller L, Truong K.-N, Helten H. Chem. Eur. J. 2018; 24: 11961

13 Riensch NA, Fritze L, Schindler T, Kremer M, Helten H. Dalton Trans. 2018; 10399

We also demonstrated B–N coupling via Si/B exchange condensation as a route to BCN hybrid polymers and oligomers; see:

14a Lorenz T, Lik A, Plamper FA, Helten H. Angew. Chem. Int. Ed. 2016; 55: 7236
14b Ayhan O, Eckert T, Plamper FA, Helten H. Angew. Chem. Int. Ed. 2016; 55: 13321
14c Helten H. Chem. Eur. J. 2016; 22: 12972
14d Lorenz T, Crumbach M, Eckert T, Lik A, Helten H. Angew. Chem. Int. Ed. 2017; 56: 2780
14e Riensch NA, Deniz A, Kühl S, Müller L, Adams A, Pich A, Helten H. Polym. Chem. 2017; 8: 5264
14f Ayhan O, Riensch NA, Glasmacher C, Helten H. Chem. Eur. J. 2018; 24: 5883

15a Mkhalid IA. I, Barnard JH, Marder TB, Murphy JM, Hartwig JF. Chem. Rev. 2010; 110: 890
15b Dudnik AS, Fu GC. J. Am. Chem. Soc. 2012; 134: 10693
15c Bagutski V, Del Grosso A, Carrillo JA, Cade IA, Helm MD, Lawson JR, Singleton PJ, Solomon SA, Marcelli T, Ingleson MJ. J. Am. Chem. Soc. 2013; 135: 474
15d Moon PJ, Halperin HM, Lundgren RJ. Angew. Chem. Int. Ed. 2016; 55: 1894
15e Zhao D, Xie Z. Angew. Chem. Int. Ed. 2016; 55: 3166

16 Cao H, Rupar PA. Chem. Eur. J. 2017; 23: 14670
17 A trimer with three furan rings could only be detected by mass spectrometry, see ref. 12b.
18 Compound 1b was generated and reacted in situ.
19 Reactions of 1b with 4a,b did not yield conclusive results, presumably because of the poor stability of 1b.
20 Ruhlandt-Senge K, Ellison JJ, Wehmschulte RJ, Pauer F, Power PP. J. Am. Chem. Soc. 1993; 115: 11353
21 Mathieu B, Ghosez L. Tetrahedron 2002; 58: 8219
22 Pearson DE, Frazer MG, Frazer VS, Washburn LC. Synthesis 1976; 621
23 Determined by HSQC (see the Supporting Information, Figure S20).

Supplementary Material

Supporting Information