Recent Advances in Water-Tolerance in Frustrated Lewis Pair Chemistry

Valerio Fasano; Michael J. Ingleson

doi:10.1055/s-0037-1609843

Synthesis, Table of Contents

Synthesis 2018; 50(09): 1783-1795
DOI: 10.1055/s-0037-1609843

short review

Recent Advances in Water-Tolerance in Frustrated Lewis Pair Chemistry

Valerio Fasano

School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK Email: valerio.fasano@manchester.ac.uk Email: michael.ingleson@manchester.ac.uk

,

Michael J. Ingleson *

School of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK Email: valerio.fasano@manchester.ac.uk Email: michael.ingleson@manchester.ac.uk

› Author Affiliations

Abstract

All articles of this category

Abstract

A water-tolerant frustrated Lewis pair (FLP) combines a sterically encumbered Lewis acid and Lewis base that in synergy are able to activate small molecules even in the presence of water. The main challenge introduced by water comes from its reversible coordination to the Lewis acid which causes a marked increase in the Brønsted acidity of water. Indeed, the oxophilic Lewis acids typically used in FLP chemistry form water adducts whose acidity can be comparable to that of strong Brønsted acids such as HCl, thus they can protonate the Lewis base component of the FLP. Irreversible proton transfer quenches the reactivity of both the Lewis acid and the Lewis base, precluding small molecule activation. This short review discusses the efforts to overcome water-intolerance in FLP systems, a topic that in less than five years has seen significant progress.

1 Introduction

2 Water-Tolerance (or Alcohol-Tolerance) in Carbonyl Reductions

3 Water-Tolerance with Stronger Bases

4 Water-Tolerant Non-Boron-Based Lewis Acids in FLP Chemistry

5 Conclusions

Key words

water-tolerance - frustrated Lewis pairs - Lewis acid - Lewis base - reduction

Full Text

References

References

1a Spikes GH. Fettinger JC. Power PP. J. Am. Chem. Soc. 2005; 127: 12232
1b Welch GC. San Juan JJ. Nasuda JD. Stephan DW. Science (Washington, D. C.) 2006; 314: 1124

For recent reviews on FLP chemistry see:

2a Frustrated Lewis Pairs I, Uncovering and Understanding . Stephan DW. Erker G. Springer; Heidelberg: 2013
2b Frustrated Lewis Pairs II, Expanding the Scope . Stephan DW. Erker G. Springer; Heidelberg: 2013
2c Scott DJ. Fuchter MJ. Ashley AE. Chem. Soc. Rev. 2017; 46: 5689
2d Stephan DW. Erker G. Angew. Chem. Int. Ed. 2015; 54: 6400
2e Paradies J. Synlett 2013; 24: 777
2f Stephan DW. Science (Washington, D. C.) 2016; 354: aaf7229
2g Stephan DW. J. Am. Chem. Soc. 2015; 137: 10018

For accounts of FLP chemistry in asymmetric catalysis see:

3a Shi L. Zhou Y.-G. ChemCatChem 2015; 7: 54
3b Meng W. Feng X. Du H. Acc. Chem. Res. 2018; 51: 191
3c Feng X. Du H. Tetrahedron Lett. 2014; 55: 6959

For pioneering studies on Si–H activation with B(C₆F₅)₃ see:

4a Parks DJ. Piers WE. J. Am. Chem. Soc. 1996; 118: 9440
4b Blackwell JM. Foster KL. Beck VH. Piers WE. J. Org. Chem. 1999; 64: 4887
4c Parks DJ. Blackwell JM. Piers WE. J. Org. Chem. 2000; 65: 3090
4d Blackwell JM. Sonmor ER. Scoccitti T. Piers WE. Org. Lett. 2000; 2: 3921

For subsequent notable mechanistic studies see:

4e Rendler S. Oestreich M. Angew. Chem. Int. Ed. 2008; 47: 5997
4f Hermeke J. Mewald M. Oestreich M. J. Am. Chem. Soc. 2013; 135: 17537
4g Houghton AF. Hurmalainen J. Mansikkamäki A. Piers WE. Tuononen HM. Nat. Chem. 2014; 6: 983

For pioneering studies on H₂ activation with B(C₆F₅)₃ see:

5a Chase PA. Welch GC. Jurca T. Stephan DW. Angew. Chem. Int. Ed. 2007; 46: 8050
5b Welch GC. Stephan DW. J. Am. Chem. Soc. 2007; 129: 1880
5c Spies P. Schwendemann S. Lange S. Kehr G. Fröhlich R. Erker G. Angew. Chem. Int. Ed. 2008; 47: 7543

6 Thomson JW. Hatnean JA. Hastie JJ. Pasternak A. Stephan DW. Chase PA. Org. Process Res. Dev. 2013; 17: 1287
7 Das S. Pati SK. Chem. Eur. J. 2017; 23: 1078

For Brønsted acidity of water–borane adduct see:

8a Bergquist C. Bridgewater BM. Harlan CJ. Norton JR. Friesner RA. Parkin G. J. Am. Chem. Soc. 2000; 122: 10581
8b Di Saverio A. Focante F. Camurati I. Resconi L. Beringhelli T. D’Alfonso G. Donghi D. Maggioni D. Mercandelli P. Sironi A. Inorg. Chem. 2005; 44: 5030
8c Lathem AP. Heiden ZM. Dalton Trans. 2017; 46: 5976

9a Lindqvist M. Sarnela N. Sumerin V. Chernichenko K. Leskela M. Repo T. Dalton Trans. 2012; 41: 4310
9b Longobardi LE. Tang C. Stephan DW. Dalton Trans. 2014; 43: 15723

10 Spies P. Erker G. Kehr G. Bergander K. Frohlich R. Grimme S. Stephan DW. Chem. Commun. 2007; 5072
11 Mahdi T. Stephan DW. J. Am. Chem. Soc. 2014; 136: 15809
12 Scott DJ. Fuchter MJ. Ashley AE. J. Am. Chem. Soc. 2014; 136: 15813
13 Hounjet LJ. Bannwarth C. Garon CN. Caputo CB. Grimme S. Stephan DW. Angew. Chem. Int. Ed. 2013; 52: 7492
14 Morris RH. Chem. Rev. 2016; 116: 8588
15 Scott DJ. Simmons TR. Lawrence EJ. Wildgoose GG. Fuchter MJ. Ashley AE. ACS Catal. 2015; 5: 5540
16 Gyömöre A. Bakos M. Földes T. Pápai I. Domján A. Soós T. ACS Catal. 2015; 5: 5366
17 Eros G. Mehdi H. Pápai I. Rokob T. Király P. Tárkányi G. Soós T. Angew. Chem. Int. Ed. 2010; 49: 6559
18 Eros G. Nagy K. Mehdi H. Pápai I. Nagy P. Király P. Tárkányi G. Soós T. Chem. Eur. J. 2012; 18: 574
19 Bakos M. Gyömöre A. Domján A. Soós T. Angew. Chem. Int. Ed. 2017; 56: 5217
20 Ghattas G. Bizzarri C. Hölscher M. Langanke J. Gurtler C. Leitnerb W. Subhani MA. Chem. Commun. 2017; 53: 3205
21 Fasano V. Radcliffe JE. Ingleson MJ. ACS Catal. 2016; 6: 1793

22a Doyle MP. West CT. J. J. Org. Chem. 1975; 40: 3835
22b Chen Q. Klare HF. T. Oestreich M. J. Am. Chem. Soc. 2016; 138: 7868

23 Fasano V. Ingleson MJ. Chem. Eur. J. 2017; 23: 2217
24 Tiddens MR. Gebbink RJ. M. K. Otte M. Org. Lett. 2016; 18: 3714
25 Pan Y. Chen C. Xu X. Zhao H. Han J. Li H. Xu L. Fan Q. Xiao J. Green Chem. 2018; 20: 403
26 Wilkins LC. Howard JL. Burger S. Frentzel-Beyme L. Browne DL. Melen RL. Adv. Synth. Catal. 2017; 359: 2580
27 Dorkó E. Szabó M. Kótai B. Pápai I. Domján A. Soós T. Angew. Chem. Int. Ed. 2017; 56: 9512
28 Ashley AE. Herrington TJ. Wildgoose GG. Zaher H. Thompson AL. Rees NH. Kramer T. O’Hare D. J. Am. Chem. Soc. 2011; 133: 14727
29 Scott DJ. Fuchter MJ. Ashley AE. Angew. Chem. Int. Ed. 2014; 53: 10218
30 Zhao H. Reibenspies JH. Gabbaï FP. Dalton Trans. 2013; 42: 608
31 Dryzhakov M. Hellal M. Wolf E. Falk FC. Moran J. J. Am. Chem. Soc. 2015; 137: 9555
32 Dryzhakov M. Moran J. ACS Catal. 2016; 6: 3670
33 Fasano V. Radcliffe JE. Ingleson MJ. Organometallics 2017; 36: 1623
34 For a selected example of a borane with higher Lewis acidity than B(C₆F₅)₃ see: Körte LA. Schwabedissen J. Soffner M. Blomeyer S. Reuter CG. Vishnevskiy YV. Neumann B. Stammler H.-G. Mitzel NW. Angew. Chem. Int. Ed. 2017; 56: 8578

For synthesis and application of Al(C₆F₅)₃ and derivatives in FLP chemistry see:

35a Dureen MA. Stephan DW. J. Am. Chem. Soc. 2009; 131: 8396
35b Ménard C. Stephan DW. Angew. Chem. Int. Ed. 2012; 51: 8272
35c Ménard C. Tran L. Stephan DW. Dalton Trans. 2013; 42: 13685
35d Chen J. Chen EY.-X. Dalton Trans. 2016; 45: 6105
35e Martinewski K. Holtrichter-Rößmann T. Rösener C. Hepp A. Wurthwein E.-U. Uhl W. Chem. Eur. J. 2017; 23: 6129

For the synthesis and application of Ga(C₆F₅)₃, In(C₆F₅)₃ and derivatives in FLP chemistry see:

35f Xu M. Possart J. Waked AE. Roy J. Uhl W. Stephan DW. Phil. Trans. R. Soc. A 2017; 375: 20170014 DOI: 10.1098/rsta.2017.0014
35g Uhl W. Willeke M. Hengesbach F. Hepp A. Layh M. Organometallics 2016; 35: 3701
35h Backs J. Lange M. Possart J. Wollschläger A. Mück-Lichtenfeld C. Uhl W. Angew. Chem. Int. Ed. 2017; 56: 3094

For the application of carbon Lewis acids in FLP chemistry see:

36a Frey GD. Lavallo V. Donnadieu B. Schoeller WW. Bertrand G. Science (Washington, D. C.) 2007; 316: 439
36b Ines B. Holle S. Goddard R. Alcarazo M. Angew. Chem. Int. Ed. 2010; 49: 8389
36c Runyon JW. Steinhof O. Rasika Dias HV. Calabrese JC. Marshall WJ. Arduengo AJ. III. Aust. J. Chem. 2011; 64: 1165
36d Boone MP. Stephan DW. J. Am. Chem. Soc. 2013; 135: 8508
36e Clark ER. Ingleson MJ. Organometallics 2013; 32: 6712
36f Kalz KF. Brinkmeier A. Dechert S. Mata RA. Meyer F. J. Am. Chem. Soc. 2014; 136: 16626
36g Auth J. Padevet J. Mauleon P. Pfaltz A. Angew. Chem. Int. Ed. 2015; 54: 9542
36h Radcliffe JE. Dunsford JJ. Cid J. Fasano V. Ingleson MJ. Organometallics 2017; 36: 4952

37a Naidu VR. Ni S. Franzen J. ChemCatChem 2015; 7: 1896
37b Zhou J. Cao LL. Liu L. Stephan DW. Dalton Trans. 2017; 46: 9334
37c Follet E. Mayer P. Stephenson DS. Ofial AR. Berionni G. Chem. Eur. J. 2017; 23: 7422

38 Brauman JI. Archie WC. Jr. J. Am. Chem. Soc. 1970; 92: 5981
39 Mosaferi E. Ripsman D. Stephan DW. Chem. Commun. 2016; 52: 8291

40a Lambert JB. Kania L. Zhang S. Chem. Rev. 1995; 95: 1191
40b Reed CA. Acc. Chem. Res. 1998; 31: 325
40c Klare HF. T. Oestreich M. Dalton Trans. 2010; 39: 9176

41 Fasano V. Radcliffe JE. Curless LD. Ingleson MJ. Chem. Eur. J. 2017; 23: 187
42 Clark ER. Ingleson MJ. Angew. Chem. Int. Ed. 2014; 53: 11306
43 Fasano V. Curless LD. Radcliffe JE. Ingleson MJ. Angew. Chem. Int. Ed. 2017; 56: 9202
44 Scott DJ. Phillips NA. Sapsford JS. Deacy AC. Fuchter MJ. Ashley AE. Angew. Chem. Int. Ed. 2016; 55: 14738
45 Whittell GR. Balmond EI. Robertson AP. M. Patra SK. Haddow MF. Manners I. Eur. J. Inorg. Chem. 2010; 3967
46 Sapsford JS. Scott DJ. Allcock NJ. Fuchter MJ. Tighe CJ. Ashley AE. Adv. Synth. Catal. 2018; in press ; DOI: 10.1002/adsc.201701418
47 Caputo CB. Hounjet LJ. Dobrovetsky R. Stephan DW. Science (Washington, D. C.) 2013; 341: 1374

For recent reviews on EPCs see:

48a Stephan DW. Angew. Chem. Int. Ed. 2017; 56: 5984
48b Bayne JM. Stephan DW. Chem. Soc. Rev. 2016; 45: 765

49a Postle S. Podgorny V. Stephan DW. Dalton Trans. 2016; 45: 14651
49b LaFortune JH. W. Johnstone TC. Perez M. Winkelhaus D. Podgorny V. Stephan DW. Dalton Trans. 2016; 45: 18156

50 Fasano V. LaFortune JH. W. Bayne JM. Ingleson MJ. Stephan DW. Chem. Commun. 2018; 54: 662
51 Pan B. Gabbaï FP. J. Am. Chem. Soc. 2014; 136: 9564

52a Ke I.-S. Myahkostupov M. Castellano FN. Gabbaï FP. J. Am. Chem. Soc. 2012; 134: 15309

For fluoride ion complexation and sensing using water-tolerant boranes see:

52b Wade CR. Broomsgrove AE. J. Aldridge S. Gabbaï FP. Chem. Rev. 2010; 110: 3958

53 For another work on water-tolerant Lewis acids not employed in FLP chemistry see: Kobayashi S. Ogawa C. Chem. Eur. J. 2006; 12: 5954