Yttrium-Catalyzed Regioselective Aminolysis of 2,3-Epoxy Esters and Amides

Dedicated to 80^th birthday of Professor Hisashi Yamamoto.

Abstract

Herein, an yttrium-catalyzed regioselective ring-opening reaction of 2,3-epoxy esters and amides with amines as nucleophiles is presented. This method features high regiocontrol, an enantiospecific S_N2 reaction pathway, a broad substrate scope, and mild reaction conditions, furnishing a wide range of α-hydroxy β-amino esters and amides in regioisomerically pure forms. Notably, the selective nucleophilic attack to the C-3 position is controlled by the directing effect of the carbonyl group of the substrates.

Key words

yttrium catalysis - epoxides - regioselectivity - aminolysis - ring opening

Publikationsverlauf

Eingereicht: 29. März 2023

Angenommen nach Revision: 19. April 2023

Accepted Manuscript online:
19. April 2023

Artikel online veröffentlicht:
22. Mai 2023

• References and Notes


For general reviews on nucleophilic ring-opening reactions of epoxides, see:
• 1a Jacobsen E. Acc. Chem. Res. 2000; 33: 421
• 1b Pastor MI, Yus M. Curr. Org. Chem. 2005; 9: 1
• 1c Schneider C. Synthesis 2006; 3919
• 1d Pineschi M. Eur. J. Org. Chem. 2006; 2006: 4979
• 1e Huang C.-Y (D.), Doyle AG. Chem. Rev. 2014; 114: 8153
• 1f Rotstein BH, Zaretsky S, Rai V, Yudin AK. Chem. Rev. 2014; 114: 8323
• 1g Saddique FA, Zahoor AF, Faiz S, Naqvi SA. R, Usman M, Ahmad M. Synth. Commun. 2016; 46: 831
• 1h Meninno S, Lattanzi A. Chem. Eur. J. 2016; 22: 3632
• 1i Hubbell AK, Coates GW. J. Org. Chem. 2020; 85: 13391

For selected examples on regioselective ring opening of sterically or electronically biased epoxides without directing groups, see:
• 2a Tokunaga M, Larrow JF, Kakiuchi F, Jacobsen E. Science 1997; 277: 936
• 2b Ready JM, Jacobsen EN. J. Am. Chem. Soc. 1999; 121: 6086
• 2c Schaus SE, Brandes BD, Larrow JF, Tokunaga M, Hansen KB, Gould AE, Furrow ME, Jacobsen EN. J. Am. Chem. Soc. 2002; 124: 1307
• 2d Bandini M, Cozzi PG, Melchiorre P, Umani-Ronchi A. Angew. Chem. Int. Ed. 2004; 43: 84
• 2e Rodríguez JR, Navarro A. Tetrahedron Lett. 2004; 45: 7495
• 2f Sundararajan G, Vijayakrishna K, Varghese B. Tetrahedron Lett. 2004; 45: 8253
• 2g Su W, Chen J, Wu H, Jin C. J. Org. Chem. 2007; 72: 4524
• 2h Wang T, Ji W.-H, Xu Z.-Y, Zeng B.-B. Synlett 2009; 1511
• 2i Li Y, Hao H.-D, Wu Y. Org. Lett. 2009; 11: 2691
• 2j Sobhani S, Vafaee A. Tetrahedron 2009; 65: 7691
• 2k Zhang Q, Nguyen HM. Chem. Sci. 2014; 5: 291
• 2l Wang Z, Kuninobu Y, Kanai M. J. Am. Chem. Soc. 2015; 137: 6140
• 2m Cheng G, Li T.-J, Yu J.-Q. J. Am. Chem. Soc. 2015; 137: 10950
• 2n Huang T, Lin L, Hu X, Zheng J, Liu X, Feng X. Chem. Commun. 2015; 51: 11374
• 2o Jamieson ML, Hume PA, Furkert DP, Brimble MA. Org. Lett. 2016; 18: 468
• 2p Wenz J, Wadepohl H, Gade LH. Chem. Commun. 2017; 53: 4308
• 2q Zhu G, Bao G, Li Y, Sun W, Li J, Hong L, Wang R. Angew. Chem. Int. Ed. 2017; 56: 5332
• 2r Xu S, Takamatsu K, Hirano K, Miura M. Angew. Chem. Int. Ed. 2018; 57: 11797
• 2s Liu W, Spannenberg A, Junge K, Beller M. Nat. Catal. 2019; 2: 523
• 2t Yao C, Dahmen CT, Gansäuer A, Norton J. Science 2019; 364: 764

For selected examples of desymmetrization of meso-epoxides, see:
• 3a Nugent WA. J. Am. Chem. Soc. 1992; 114: 2768
• 3b Martínez LE, Leighton JL, Carsten DH, Jacobsen EN. J. Am. Chem. Soc. 1995; 117: 5897
• 3c Iida T, Yamamoto N, Sasai H, Shibasaki M. J. Am. Chem. Soc. 1997; 119: 4783
• 3d Iida T, Yamamoto N, Matsunaga S, Woo H.-G, Shibasaki M. Angew. Chem. Int. Ed. 1998; 37: 2223
• 3e Tao B, Lo MM.-C, Fu GC. J. Am. Chem. Soc. 2001; 123: 353
• 3f Ready JM, Jacobsen EN. Angew. Chem. Int. Ed. 2002; 41: 1374
• 3g Schneider C, Sreekanth AR, Mai E. Angew. Chem. Int. Ed. 2004; 43: 5691
• 3h Zhao L, Han B, Huang Z, Miller M, Huang H, Malashock DS, Zhu Z, Milan A, Robertson DE, Weiner DP, Burk MJ. J. Am. Chem. Soc. 2004; 126: 11156
• 3i Arai K, Lucarini S, Salter MM, Ohta K, Yamashita Y, Kobayashi S. J. Am. Chem. Soc. 2007; 129: 8103
• 3j Arai K, Salter MM, Yamashita Y, Kobayashi S. Angew. Chem. Int. Ed. 2007; 46: 955
• 3k Pu X, Qi X, Ready JM. J. Am. Chem. Soc. 2009; 131: 10364
• 3l Kalow JA, Doyle AG. J. Am. Chem. Soc. 2010; 132: 3268
• 3m Wang Z, Law WK, Sun J. Org. Lett. 2013; 15: 5964
• 3n Monaco MR, Prévost S, List B. J. Am. Chem. Soc. 2014; 136: 16982
• 3o Monaco MR, Prévost S, List B. Angew. Chem. Int. Ed. 2014; 53: 8142

For reviews on organic reactions involving directing groups, see:
• 4a Hoveyda AH, Evans DA, Fu GC. Chem. Rev. 1993; 93: 1307
• 4b Rousseau G, Breit B. Angew. Chem. Int. Ed. 2011; 50: 2450
• 4c Sawano T, Yamamoto H. J. Org. Chem. 2018; 83: 4889
• 4d Bhadra S, Yamamoto H. Chem. Rev. 2018; 118: 3391
• 5 For a review on the directed regioselective nucleophilic ring opening of epoxides, see: Wang C, Luo L, Yamamoto H. Acc. Chem. Res. 2016; 49: 193

For selected examples of catalytic hydroxy or sulfonamide-directed nucleophilic ring opening of epoxides or aziridines, see:
• 6a Wang C, Yamamoto H. J. Am. Chem. Soc. 2014; 136: 6888
• 6b Wang C, Yamamoto H. Angew. Chem. Int. Ed. 2014; 53: 13920
• 6c Uesugi S.-i, Watanabe T, Imaizumi T, Shibuya M, Kanoh N, Iwabuchi Y. Org. Lett. 2014; 16: 4408
• 6d Wang C, Yamamoto H. Org. Lett. 2014; 16: 5937
• 6e Wang C, Yamamoto H. J. Am. Chem. Soc. 2015; 137: 4308
• 6f Zhang Y.-Q, Funken N, Winterscheid P, Gansäuer A. Angew. Chem. Int. Ed. 2015; 54: 6931
• 6g Wang C, Yamamoto H. Angew. Chem. Int. Ed. 2015; 54: 8760
• 6h Tanveer K, Jarrah K, Taylor MS. Org. Lett. 2015; 17: 3482
• 6i Zhang Y.-Q, Poppel C, Panfilova A, Bohle F, Grimme S, Gansäuer A. Angew. Chem. Int. Ed. 2017; 56: 9719
• 6j Garrett GE, Tanveer K, Taylor MS. J. Org. Chem. 2017; 82: 1085
• 6k Fan P, Su S, Wang C. ACS Catal. 2018; 8: 6820
• 6l Liu J, Yao H, Wang C. ACS Catal. 2018; 8: 9376
• 6m Wang G, Garrett GE, Taylor MS. Org. Lett. 2018; 20: 5375
• 6n Su S, Wang C. Org. Lett. 2019; 21: 2436
• 6o Fan P, Wang C. Commun. Chem. 2019; 2: 104
• 6p Yao H, Liu J, Wang C. Org. Biomol. Chem. 2019; 17: 1901
• 6q Nakamura D, Sasano Y, Iwabuchi Y. Org. Biomol. Chem. 2019; 17: 3581
• 6r Wang G, Taylor MS. Adv. Synth. Catal. 2020; 362: 398
• 6s Liu J, Wang C. ACS Catal. 2020; 10: 556
• 6t Desai SP, Taylor MS. Org. Lett. 2021; 23: 7049

For selected examples of hydroxy-directed nucleophilic ring opening of epoxides or aziridines using stoichiometric promotors, see:
• 7a Johnson MR, Nakata T, Kishi Y. Tetrahedron Lett. 1979; 20: 4343
• 7b Suzuki T, Saimoto H, Tomioka H, Oshima K, Nozaki H. Tetrahedron Lett. 1982; 23: 3597
• 7c Caron M, Sharpless KB. J. Org. Chem. 1985; 50: 1557
• 7d Maruoka K, Sano H, Yamamoto H. Chem. Lett. 1985; 14: 599
• 7e Chong JM, Cyr DR, Mar EK. Tetrahedron Lett. 1987; 28: 5009
• 7f Caron M, Carlier PR, Sharpless KB. J. Org. Chem. 1988; 53: 5185
• 7g Bonini C, Righi G, Sotgiu G. J. Org. Chem. 1991; 56: 6206
• 7h Canas M, Poch M, Verdaguer X, Moyano A, Pericàs MA. Riera A. Tetrahedron Lett. 1991; 32: 6931
• 7i Chini M, Crotti P, Flippin LA, Gardelli C, Giovani E, Macchia F, Pineschi M. J. Org. Chem. 1993; 58: 1221
• 7j Tomata Y, Sasaki M, Tanino K, Miyashita M. Org. Lett. 2001; 3: 1765
• 7k Sasaki M, Tanino K, Miyashita M. Tetrahedron Lett. 2003; 44: 8975
• 7l Sasaki M, Tanino K, Hirai A, Miyashita M. Org. Lett. 2003; 5: 1789
• 7m Mukerjee P, Abid M, Schroeder FC. Org. Lett. 2010; 12: 3986
• 7n Jiang H, Xu L.-P, Fang Y, Zhang Z.-X, Yang Z, Huang Y. Angew. Chem. Int. Ed. 2016; 55: 14340
• 7o Zhang Y.-Q, Bohle F, Bleith R, Schnakenburg G, Grimme S, Gansäuer A. Angew. Chem. Int. Ed. 2018; 57: 13528
• 8 Chong JM, Sharpless KB. J. Org. Chem. 1985; 50: 1560
• 9 For an isolated example of a Y-catalyzed ring opening of an epoxy ester, see: Natongchai W, Kahn RA, Alsalme A, Shaikh RR. Catalysts 2017; 7: 340
• 10 Ethyl (±)-erythro-3-[(3-Bromophenyl)amino]-2-hydroxy-5-phenylpentanoate (3ae); Typical Procedure To a suspension of the Y(OTf)₃ (16.1 mg, 0.03 mmol, 15 mol%) in THF (0.5 mL) were added the amine 2e (34.2 mg, 0.2 mmol, 1.0 equiv) and the epoxide 1a (66.0 mg, 0.3 mmol, 1.5 equiv) at rt. The resulting mixture was heated to 60 °C and stirred at this temperature for 24 h. The mixture was then cooled to rt, and the solvent was removed in vacuum. The residue was purified by column chromatography [silica gel, PE–EtOAc (5:1)] to give a yellow oil; yield: 65 mg (83%). ¹H NMR (400 MHz, CDCl₃): δ = 7.30–7.23( m, 2 H), 7.22–7.16 (m, 1 H), 7.13–7.08 (m, 2 H), 7.01 (t, J = 8.0 Hz, 1 H), 6.84 (ddd, J = 7.9, 1.9, 0.9 Hz, 1 H), 6.77 (t, J = 2.1 Hz, 1 H), 6.53 (ddd, J = 8.2, 2.4, 0.9 Hz, 1 H), 4.38–4.27 (m, 1 H), 4.19 (q, J = 7.1 Hz, 2 H), 3.96 (d, J = 10.3 Hz, 1 H), 3.73–3.64 (br s, 1 H), 2.93 (d, J = 5.5 Hz, 1 H), 2.87–2.75 (m, 1 H), 2.73–2.55 (m, 1 H), 1.93–1.79 (m, 1 H), 1.67–1.57 (m, 1 H), 1.22 (t, J = 7.1 Hz, 3 H). ¹³C NMR (101 MHz, CDCl₃): δ = 173.4, 148.5, 141.3, 130.7, 128.5 (4 C), 126.1, 123.4 , 120.8, 116.6, 112.5, 71.3, 62.1, 54.6, 32.1, 31.3, 14.2. HRMS (ESI): m/z [M + H]⁺ calcd for C₁₉H₂₃BrNO₃: 392.0856; found: 392.0866.