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2021 | OriginalPaper | Chapter

2. Frustrated Lewis Pair Catalyzed Asymmetric Reactions

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Authors: Xiangqing Feng, Wei Meng, Haifeng Du

Publisher: Springer International Publishing

Published in: Frustrated Lewis Pairs

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Abstract

As a lately emerging area, frustrated Lewis pair chemistry provides the most effective way for metal-free catalytic reductions, and a wide range of unsaturated compounds have been successfully reduced. However, the asymmetric catalytic reduction is still in its initial stage, and some formidable challenges still remain. The development of highly effective chiral FLP catalysts and their applications in asymmetric catalysis are two very important subjects in this field. This chapter will summarize the advances for chiral FLP catalysts and metal-free asymmetric reductions including hydrogenations, Piers-type hydrosilylations, and transfer hydrogenations in the past six years.

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Welch GC et al (2006) Reversible, Metal-Free Hydrogen Activation. Science 314(5802):1124–1126. https://doi.org/10.1126/science.1134230

Kenward AL, Piers WE (2008) Heterolytic H ₂ Activation by Nonmetals. Angew Chem Int Ed 47:38–41. https://doi.org/10.1002/anie.200702816

Stephan DW (2009) Frustrated Lewis Pairs: a New Strategy to Small Molecule Activation and Hydrogenation Catalysis. Dalton Trans 3129–3136. https://doi.org/10.1039/B819621D

Stephan DW, Erker G (2010) Frustrated Lewis Pairs: Metal-Free Hydrogen Activation and More. Angew Chem Int Ed 49:46–76. https://doi.org/10.1002/anie.200903708

Erker G (2011) Organometallic Frustrated Lewis Pair Chemistry. Dalton Trans 40:7475–7483. https://doi.org/10.1039/C1DT10152H

Soós T (2011) Design of Frustrated Lewis Pair Catalysts for Metal-Free and Selective Hydrogenation. Pure Appl Chem 83:667–675. https://doi.org/10.1351/PAC-CON-11-01-02

Erker G (2012) Frustrated Lewis Pairs: Some Recent Developments. Pure Appl Chem 84:2203–2217. https://doi.org/10.1351/PAC-CON-12-04-07

Paradies J (2014) Metal-Free Hydrogenation of Unsaturated Hydrocarbons Employing Molecular Hydrogen. Angew Chem Int Ed 53:3552–3557. https://doi.org/10.1002/anie.201309253

Stephan DW, Erker G (2015) Frustrated Lewis Pair Chemistry: Development and Perspectives. Angew Chem Int Ed 54:6400–6441. https://doi.org/10.1002/anie.201409800

10.

Oestreich M, Hermeke J, Mohr J (2015) A Unified Survey of Si–H and H–H Bond Activation Catalysed by Electron-Deficient Boranes. Chem Soc Rev 44:2202–2220. https://doi.org/10.1039/C4CS00451E

11.

Stephan DW (2015) Frustrated Lewis Pairs: From Concept to Catalysis. Acc Chem Res 48:306–316. https://doi.org/10.1021/ar500375j

12.

Scott DJ, Fuchter MJ, Ashley AE (2017) Designing Effective “Frustrated Lewis Pair” Hydrogenation Catalysts. Chem Soc Rev 46:5689–5700. https://doi.org/10.1039/C7CS00154A

13.

Liu Y, Du H (2014) Frustrated Lewis Pair Catalyzed Asymmetric Hydrogenation. Acta Chim Sinica 72:771–777. https://doi.org/10.6023/A14040344

14.

Feng X, Du H (2014) Metal-Free Asymmetric Hydrogenation and Hydrosilylation Catalyzed by Frustrated Lewis Pairs. Tetrahedron Lett 55:6959–6964. https://doi.org/10.1016/j.tetlet.2014.10.138

15.

Shi L, Zhou Y-G (2015) Enantioselective Metal-Free Hydrogenation Catalyzed by Chiral Frustrated Lewis Pairs. ChemCatChem 7:54–56. https://doi.org/10.1002/cctc.201402838

16.

Wilkins LC, Melen RL (2016) Enantioselective Main Group Catalysis: Modern Catalysts for Organic Transformations. Coord Chem Rev 324:123–139. https://doi.org/10.1016/j.ccr.2016.07.011

17.

Paradies J (2018) Chiral Borane-Based Lewis Acids for Metal Free Hydrogenations. Top Organomet Chem 62:193–216. https://doi.org/10.1007/3418_2016_173

18.

Meng W, Feng X, Du H (2018) Frustrated Lewis Pairs Catalyzed Asymmetric Metal-Free Hydrogenations and Hydrosilylations. Acc Chem Res 51:191–201. https://doi.org/10.1021/acs.accounts.7b00530

19.

Chen D, Klankermayer J (2008) Metal-Free Catalytic Hydrogenation of Imines with Tris(perfluorophenyl)borane. Chem Commun 18:2130–2131. https://doi.org/10.1039/B801806E

20.

Chen D, Wang Y, Klankermayer J (2010) Enantioselective Hydrogenation with Chiral Frustrated Lewis Pairs. Angew Chem Int Ed 49:9475–9478. https://doi.org/10.1002/anie.201004525

21.

Sumerin V, Chernichenko K, Nieger M, Leskelä M, Rieger B, Repo T (2011) Highly Active Metal-Free Catalysts for Hydrogenation of Unsaturated Nitrogen-Containing Compounds. Adv Synth Catal 353:2093–2110. https://doi.org/10.1002/adsc.201100206

22.

Ghattas G, Chen D, Pan F, Klankermayer J (2012) Asymmetric Hydrogenation of Imines with a Recyclable Chiral Frustrated Lewis Pair Catalyst. Dalton Trans 41:9026–9028. https://doi.org/10.1039/C2DT30536D

23.

Heiden ZM, Stephan DW (2011) Metal-Free Diastereoselective Catalytic Hydrogenations of Imines Using B(C ₆F ₅) ₃. Chem Commun 47:5729–5731. https://doi.org/10.1039/C1CC10438A

24.

Chen D, Leich V, Pan F, Klankermayer J (2012) Enantioselective Hydrosilylation with Chiral Frustrated Lewis Pairs. Chem Eur J 18:5184–5187. https://doi.org/10.1002/chem.201200244

25.

Mewald M, Fröhlich R, Oestreich M (2011) An Axially Chiral, Electron-Deficient Borane: Synthesis, Coordination Chemistry, Lewis Acidity, and Reactivity. Chem Eur J 17:9406–9414. https://doi.org/10.1002/chem.201100724

26.

Mewald M, Oestreich M (2012) Illuminating the Mechanism of the Borane-Catalyzed Hydrosilylation of Imines with Both an Axially Chiral Borane and Silane. Chem Eur J 18:14079–14084. https://doi.org/10.1002/chem.201202693

27.

Parks DJ, Piers WE, Yap GPA (1998) Synthesis, Properties, and Hydroboration Activity of the Highly Electrophilic Borane Bis(pentafluorophenyl)borane, HB(C ₆F ₅) ₂. Organometallics 17:5492–5503. https://doi.org/10.1021/om980673e

28.

Liu Y, Du H (2013) Chiral Dienes as “Ligands” for Borane-Catalyzed Metal-Free Asymmetric Hydrogenation of Imines. J Am Chem Soc 135:6810–6813. https://doi.org/10.1021/ja4025808

29.

Cao Z, Du H (2010) Development of Binaphthyl-Based Chiral Dienes for Rh(I)-Catalyzed Asymmetrc Arylation of N, N-Dimethylsulamoyl-Protected Aldimines. Org Lett 12:2602–2605. https://doi.org/10.1021/ol1008087

30.

Lindqvist M, Borre K, Axenov K, Kótai B, Nieger M, Leskelä M, Pápai I, Repo T (2015) Chiral Molecular Tweezers: Synthesis and Reactivity in Asymmetric Hydrogenation. J Am Chem Soc 137:4038–4041. https://doi.org/10.1021/ja512658m

31.

Wang X, Kehr G, Daniliuc CG, Erker G (2014) Internal Adduct Formation of Active Intramolecular C ₄-Bridged Frustrated Phosphane/Borane Lewis Pairs. J Am Chem Soc 136:3293–3303. https://doi.org/10.1021/ja413060u

32.

Ye K-Y, Wang X, Daniliuc CG, Kehr G, Erker G (2017) A Ferrocene-Based Phosphane/Borane Frustrated Lewis Pair for Asymmetric Imine Reduction. Eur J Inorg Chem 368–371. https://doi.org/10.1002/ejic.201600834

33.

Liu X, Liu T, Meng W, Du, H (2018) Asymmetric Hydrogenation of Imines with Chiral Alkene-Derived Boron Lewis Acids. Org Biomol Chem 16:8686–8689. https://doi.org/10.1039/C8OB02446D

34.

Tu X-S, Zeng N‐N, Li R‐Y, Zhao Y‐Q, Xie D‐Z, Peng Q, Wang X‐C (2018) C ₂-Symmetric Bicyclic Bisborane Catalysts: Kinetic or Thermodynamic Products of a Reversible Hydroboration of Dienes. Angew Chem Int Ed 57:15096–15100. https://doi.org/10.1002/anie.201808289

35.

Lam J, Günther BAR, Farrell JM, Eisenberger P, Bestvater BP, Newman PD, Melen RL, Crudden CM, Stephan DW (2016) Chiral Carbene-Borane Adducts: Precursors for Borenium Catalysts for Asymmetric FLP Hydrogenations. Dalton Trans 45:15303–15316. https://doi.org/10.1039/C6DT02202B

36.

Mercea DM, Howlett MG, Piascik AD, Scott DJ, Steven A, Ashley AE, Fuchter MJ (2019) Enantioselective Reduction of N-Alkyl Ketimines with Frustrated Lewis Pair Catalysis Using Chiral Borenium Ions. Chem Commun 55:7077–7080. https://doi.org/10.1039/C9CC02900A

37.

Zhu X, Du H (2015) A Highly Stereoselective Metal-Free Hydrogenation of Diimines for the Synthesis of C is-Vicinal Diamines. Org Lett 17:3106–3109. https://doi.org/10.1021/acs.orglett.5b01380

38.

Wei S, Feng X, Du H (2016) A Metal-Free Hydrogenation of 3-Substituted 2 H-1,4-Benzoxazines. Org Biomol Chem 14:8026–8029. https://doi.org/10.1039/C6OB01556E

39.

Mahdi T, del Castillo JN, Stephan DW (2013) Metal-Free Hydrogenation of N-Based Heterocycles. Organometallics 32:1971–1978. https://doi.org/10.1021/om4000727

40.

Liu Y, Du H (2013) Metal-Free Borane-Catalyzed Highly Stereoselective Hydrogenation of Pyridines. J Am Chem Soc 135:12968–12971. https://doi.org/10.1021/ja406761j

41.

Wang W, Feng X, Du H (2016) Borane-Catalyzed Metal-Free Hydrogenation of 2,7-Disubstituted 1,8-Naphthyridines. Org Biomol Chem 14:6683–6686. https://doi.org/10.1039/C6OB01172A

42.

Zhang Z, Du H (2015) A Highly cis-Selective and Enantioselective Metal-Free Hydrogenation of 2,3-Disubstituted Quinoxalines. Angew Chem Int Ed 54:623–626. https://doi.org/10.1002/anie.201409471

43.

Zhang Z, Du H (2015) Cis-Selective and Highly Enantioselective Hydrogenation of 2,3,4-Trisubstituted Quinolines. Org Lett 17:2816–2819. https://doi.org/10.1021/acs.orglett.5b01240

44.

Zhang Z, Du H (2015) Enantioselective Metal-Free Hydrogenations of Disubstituted Quinolines. Org Lett 17:6266–6269. https://doi.org/10.1021/acs.orglett.5b03307

45.

Han C, Zhang E, Feng X, Wang S, Du H (2018) B(C ₆F ₅) ₃-Catalyzed Metal-Free Hydrogenations of 2-Quinolinecarboxylates. Tetrahedron Lett 59:1400–1403. https://doi.org/10.1016/j.tetlet.2018.02.057

46.

Li X, Tian J‐J, Liu N, Tu X‐S, Zeng N‐N, Wang X‐C (2019) Spiro-Bicyclic Bisborane Catalysts for Metal-Free Chemoselective and Enantioselective Hydrogenation of Quinolines. Angew Chem Int Ed 58:4664–4668. https://doi.org/10.1002/anie.201900907

47.

Wang H, Fröhlich R, Kehr G, Erker G (2008) Heterolytic Dihydrogen Activation with the 1,8-Bis(diphenylphosphino)naphthalene/B(C ₆F ₅) ₃ Pair and Its Application for Metal-Free Catalytic Hydrogenation of Silyl Enol Ethers. Chem Commun 5966–5968. https://doi.org/10.1039/B813286K

48.

Wei S, Du H (2014) A Highly Enantioselective Hydrogenation of Silyl Enol Ethers Catalyzed by Chiral Frustrated Lewis Pairs. J Am Chem Soc 136:12261–12264. https://doi.org/10.1021/ja507536n

49.

Ren X, Li G, Wei S, Du H (2015) Facile Development of Chiral Alkenylboranes from Chiral Diynes for Asymmetric Hydrogenation of Silyl Enol Ethers. Org Lett 17:990–993. https://doi.org/10.1021/acs.orglett.5b00085

50.

Mahdi T, Stephan DW (2014) Enabling Catalytic Ketone Hydrogenation by Frustrated Lewis Pairs. J Am Chem Soc 136:15809–15812. https://doi.org/10.1021/ja508829x

51.

Scott DJ, Fuchter MJ, Ashley AE (2014) Nonmetal Catalyzed Hydrogenation of Carbonyl Compounds. J Am Chem Soc 136: 15813–15816. https://doi.org/10.1021/ja5088979

52.

Gao B, Feng X, Meng W, Du H (2020) Asymmetric Hydrogenations of Ketones and Enones with Chiral Lewis Base Derived Frustrated Lewis Pairs. Angew Chem Int Ed 59:4498–4504. https://doi.org/10.1002/anie.201914568

53.

Parks DJ, Piers WE (1996) Tris(pentafluorophenyl)boron-Catalyzed Hydrosilation of Aromatic Aldehydes, Ketones, and Esters. J Am Chem Soc 118:9440–9441. https://doi.org/10.1021/ja961536g

54.

Zhu X, Du H (2015) A Chiral Borane Catalyzed Asymmetric Hydrosilylation of Imines. Org Biomol Chem 13:1013–1016. https://doi.org/10.1039/C4OB02419B

55.

Ren X, Du H (2016) Chiral Frustrated Lewis Pairs Catalyzed Highly Enantioselective Hydrosilylations of 1,2-Dicarbonyl Compounds. J Am Chem Soc 138:810–813. https://doi.org/10.1021/jacs.5b13104

56.

Süsse L, Hermeke J, Oestreich M (2016) The Asymmetric Piers Hydrosilylation. J Am Chem Soc 138:6940−6943. https://doi.org/10.1021/jacs.6b03443

57.

Liu X, Wang Q, Han C, Feng X, Du H (2019) Chiral Frustrated Lewis Pairs Catalyzed Highly Enantioselective Hydrosilylations of Ketones. Chin J Chem 37:663–666. https://doi.org/10.1002/cjoc.201900121

58.

Wang Q, Han C, Feng X, Du H (2019) Chiral Spiro Dienes Derived Boranes for Asymmetric Hydrosilylation of Ketones. Chin J Org Chem 39:2257–2263. https://doi.org/10.6023/cjoc201903076

59.

Ren X, Han C, Feng X, Du H (2017) A Borane-Catalyzed Metal-Free Hydrosilylation of Chromones and Flavones. Synlett 28:2421–2424. https://doi.org/10.1055/s-0036-1588474

60.

Pan Y, Chen C, Xu X, Zhao H, Han J, Li H, Xu L, Fan Q, Xiao J (2018) Metal-Free Tandem Cyclization/Hydrosilylation to Construct Tetrahydroquinoxalines. Green Chem 20:403–411. https://doi.org/10.1039/C7GC03095A

61.

Li S, Li G, Meng W, Du H (2016) A Frustrated Lewis Pair Catalyzed Asymmetric Transfer Hydrogenation of Imines Using Ammonia Borane. J Am Chem Soc 138:12956–12962. https://doi.org/10.1021/jacs.6b07245

62.

Li S, Meng W, Du H (2017) Asymmetric Transfer Hydrogenations of 2,3-Disubstituted Quinoxalines with Ammonia Borane. Org Lett 19:2604–2606. https://doi.org/10.1021/acs.orglett.7b00935

63.

Zhao W, Feng Q, Yang J, Du H (2019) Asymmetric Transfer Hydrogenations of β- N-Substituted Enamino Esters with Ammonia Borane. Tetrahedron Lett 60:1193–1196. https://doi.org/10.1016/j.tetlet.2019.03.060

64.

Wang Q, Chem J, Feng X, Du H (2018) B(C ₆F ₅) ₃-Catalyzed Transfer Hydrogenations of Imines with Hantzsch Esters. Org Biomol Chem 16:1448–1451. https://doi.org/10.1039/C8OB00023A

65.

Shang M, Wang X, Moh Koo S, Youn J, Chan JZ, Yao W, Hastings BT, Wasa M (2017) Frustrated Lewis Acid/Brønsted Base Catalysts for Direct Enantioselective α-Amination of Carbonyl Compounds. J Am Chem Soc 139:95−98. https://doi.org/10.1021/jacs.6b11908

66.

Chan JZ, Yao W, Hastings BT, Lok CK, Wasa M (2016) Direct Mannich-Type Reactions Promoted by Frustrated Lewis Acid/Brønsted Base Catalysts. Angew Chem Int Ed 55:13877–13881. https://doi.org/10.1002/anie.201608583

67.

Shang M, Cao M, Wang Q, Wasa M (2017) Enantioselective Direct Mannich-Type Reactions Catalyzed by Frustrated Lewis Acid/Brønsted Base Complexes. Angew Chem Int Ed 56:13338–13341. https://doi.org/10.1002/anie.201708103

Title

Frustrated Lewis Pair Catalyzed Asymmetric Reactions

Book

Frustrated Lewis Pairs

Print ISBN: 978-3-030-58887-8

Electronic ISBN: 978-3-030-58888-5

https://doi.org/10.1007/978-3-030-58888-5

DOI

https://doi.org/10.1007/978-3-030-58888-5_2

Authors:

Xiangqing Feng
Wei Meng
Haifeng Du

Publisher

Springer International Publishing

Sequence number

Chapter number

Chapter 2

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