(S)-Proline-Derived Catalysts for the Acylative Kinetic Resolution of Alcohols: A Remote Structural Change Allows a Complete Selectivity Switch

Oliver Gleeson; Yurii K. Gun’ko; Stephen J. Connon

doi:10.1055/s-0033-1339286

Synlett, Table of Contents

Synlett 2013; 24(13): 1728-1734
DOI: 10.1055/s-0033-1339286

letter

(S)-Proline-Derived Catalysts for the Acylative Kinetic Resolution of Alcohols: A Remote Structural Change Allows a Complete Selectivity Switch

Oliver Gleeson

Trinity Biomedical Sciences Institute, School of Chemistry, The University of Dublin, Trinity College, Dublin 2, Ireland Fax: +353(1)6712826 Email: connons@tcd.ie

,

Yurii K. Gun’ko

Trinity Biomedical Sciences Institute, School of Chemistry, The University of Dublin, Trinity College, Dublin 2, Ireland Fax: +353(1)6712826 Email: connons@tcd.ie

,

Stephen J. Connon*

Trinity Biomedical Sciences Institute, School of Chemistry, The University of Dublin, Trinity College, Dublin 2, Ireland Fax: +353(1)6712826 Email: connons@tcd.ie

› Author Affiliations

Abstract

All articles of this category

Abstract

A systematic preliminary study has identified a suite of catalysts, all readily prepared and derived from (S)-proline, which differ by a remote substituent only. If this substituent is capable of hydrogen-bond donation the catalyst will promote the resolution of secondary alcohols with the opposite sense of enantiodiscrimination to that observed when the substituent is capable of accepting hydrogen bonds.

Key words

amines - acylation - alcohols - nucleophiles - kinetic resolution

Full Text

References

References and Notes

For selected reviews, see:

1a Chen C.-S, Sih C. Angew. Chem. Int. Ed. 1989; 28: 695
1b Theil F. Chem. Rev. 1995; 95: 2203

For recent reviews, see:

2a Connon SJ. Lett. Org. Chem. 2006; 3: 333
2b Wurz RP. Chem. Rev. 2007; 107: 5570
2c Denmark SE, Beutner GL. Angew. Chem. Int. Ed. 2008; 47: 1560
2d Spivey AC, Arseniyadis S. Top. Curr. Chem. 2010; 291: 233
2e Müller CE, Schreiner PR. Angew. Chem. Int. Ed. 2011; 50: 6012
2f Pellissier H. Adv. Synth. Catal. 2011; 353: 1613

For examples, see:

3a Vedejs E, Daugulis O, Diver ST. J. Org. Chem. 1996; 61: 430
3b Vedejs E, Daugulis O. J. Am. Chem. Soc. 1999; 121: 5813
3c Vedejs E, Daugulis O. J. Am. Chem. Soc. 2003; 125: 4166
3d MacKay JA, Vedejs E. J. Org. Chem. 2004; 69: 6934

4 Mizuta S, Sadamori M, Fujimoto T, Yamamoto I. Angew. Chem. Int. Ed. 2003; 42: 3383

For representative examples, see:

5a Vedejs E, Chen X. J. Am. Chem. Soc. 1996; 118: 1809
5b Kawabata T, Nagato M, Takasu K, Fuji K. J. Am. Chem. Soc. 1997; 119: 3169
5c Ruble JC, Tweddell J, Fu GC. J. Org. Chem. 1998; 63: 2794
5d Spivey AC, Fekner T, Adams H. Tetrahedron Lett. 1998; 39: 8919
5e Tao B, Ruble JC, Hoic DA, Fu GC. J. Am. Chem. Soc. 1999; 121: 5091
5f Tao B, Ruble JC, Hoic DA, Fu GC. J. Am. Chem. Soc. 1999; 121: 10452
5g Spivey AC, Fekner T, Spey SE, Adams H. J. Org. Chem. 1999; 64: 9430
5h Spivey AC, Maddaford A, Fekner T, Redgrave AJ, Frampton CS. J. Chem. Soc., Perkin Trans. 1 2000; 3460
5i Naraku G, Shimomoto N, Hanamoto T, Inanaga J. Enantiomer 2000; 5: 135
5j Kawabata T, Yamamoto K, Momose Y, Yoshida H, Nagaoka Y, Fuji K. Chem. Commun. 2001; 2700
5k Jeong K.-S, Kim S.-H, Park H.-J, Chang K.-J, Kim KS. Chem. Lett. 2002; 1114
5l Priem G, Anson MS, Macdonald SJ. F, Pelotier B, Campbell IB. Tetrahedron Lett. 2002; 43: 6001
5m Seitzberger JG, Dissing C, Søtofte I, Norrby P.-O, Johannsen M. J. Org. Chem. 2005; 70: 8332
5n Yamada S, Misono T, Iwai Y. Tetrahedron Lett. 2005; 46: 2239
5o Poisson T, Penhoat M, Papamical C, Dupas G, Dalla V, Marsais F, Levacher V. Synlett 2005; 2285
5p Nguyen HV, Butler DC. D, Richards CJ. Org. Lett. 2006; 8: 769
5q Nguyen HV, Motevalli M, Richards CJ. Synlett 2007; 725

For examples, see:

6a Miller SJ, Copeland GT, Papaioannou N, Horstmann TE, Ruel EM. J. Am. Chem. Soc. 1998; 120: 1629
6b Jarvo ER, Copeland GT, Papaioannou N, Bonitatebus PJ, Miller SJ. J. Am. Chem. Soc. 1999; 121: 11638
6c Jarvo ER, Vasbinder MM, Miller SJ. Tetrahedron 2000; 56: 9773
6d Vasbinder MM, Jarvo ER, Miller SJ. Angew. Chem. Int. Ed. 2001; 40: 2824
6e Ishihara K, Kosugi Y, Akakura M. J. Am. Chem. Soc. 2004; 126: 12212
6f Hrdina R, Müller CE, Schreiner PR. Chem. Commun. 2010; 46: 2689

For representative examples, see:

7a Birman VB, Uffman EW, Jiang H, Li X, Kilbane CJ. J. Am. Chem. Soc. 2004; 126: 12226
7b Birman VB, Jiang H. Org. Lett. 2005; 7: 3445
7c Li X, Liu P, Houk KN, Birman VB. J. Am. Chem. Soc. 2008; 130: 13836
7d Birman VB, Li X. Org. Lett. 2008; 10: 1115
7e Zhang Y, Birman VB. Adv. Synth. Catal. 2009; 351: 2525
7f Hu B, Meng M, Wang Z, Du W, Fossey JS, Hu X, Deng W.-P. J. Am. Chem. Soc. 2010; 132: 17041

For representative examples, see:

8a Oriyama T, Hori Y, Imai K, Sasaki R. Tetrahedron Lett. 1996; 37: 8543
8b Oriyama T, Imai K, Hosoya T, Sano T. Tetrahedron Lett. 1998; 39: 397
8c Oriyama T, Imai K, Sano T, Hosoya T. Tetrahedron Lett. 1998; 39: 3529

For representative examples, see:

9a Suzuki Y, Yamauchi K, Muramatsu K, Sato M. Chem. Commun. 2004; 2770
9b Suzuki Y, Muramatsu K, Yamauchi K, Morie Y, Sato M. Tetrahedron 2006; 62: 302
9c Kano T, Sasaki K, Maruoka K. Org. Lett. 2005; 7: 1347

10a O’Dálaigh C, Hynes SJ, Maher DJ, Connon SJ. Org. Biomol. Chem. 2005; 3: 981
10b O’Dálaigh C, Hynes SJ, O’Brien JE, McCabe T, Maher DJ, Watson GW, Connon SJ. Org. Biomol. Chem. 2006; 4: 2785
10c O’Dálaigh C, Connon SJ. J. Org. Chem. 2007; 72: 7066
10d Gleeson O, Tekoriute R, Gun’ko YK, Connon SJ. Chem. Eur. J. 2009; 15: 5669
10e Gleeson O, Davies G.-L, Peschiulli A, Tekoriute R, Gun’ko YK, Connon SJ. Org. Biomol. Chem. 2011; 9: 7929

11 Peschiulli A, Procuranti B, O’Connor CJ, Connon SJ. Nat. Chem. 2010; 2: 380
12 Kagan HB, Fiaud JC. Top. Stereochem. 1988; 18: 249
13 Alvarez-Pérez M, Goldup SM, Leigh DA, Slawin AM. Z. J. Am. Chem. Soc. 2008; 130: 1836
14 It is tempting to speculate that reduced access to a catalytically relevant conformation which is not the lowest energy conformation available is responsible; however a definitive explanation must await further studies.
15 The data associated with 1a, 21 and their acylated/alkylated analogues are taken from ref. 10b and are included here to facilitate analysis only.

16a General Procedure for the Acylative Kinetic Resolution of Secondary Alcohols 9, 17, 18, 19, and 20 Promoted by Catalyst 8 (Table 2): A 1 mL reaction vessel charged with catalyst 8 (5.0 mol%) and a small magnetic stirring bar was placed under an atmosphere of argon. The appropriate secondary alcohol was added followed by CH₂Cl₂ (0.20 M). After allowing the reaction mixture to equilibrate (ca. 10 min), Et₃N (1.05–2.55 equiv) was added. The resulting solution was left stirring (ca. 30 min) at –60 °C, followed by the addition of acetic anhydride (1.00–2.50 equiv) via syringe. After the reaction was complete, the reaction was quenched by the addition of MeOH (10.0 equiv). Solvents were removed in vacuo. The alcohol and its ester were separated from the catalyst by passing a concentrated solution of the crude in CH₂Cl₂ through a pad of silica gel. Analytical data for catalyst 8: mp 79–81 °C; [α]²⁰ _D –191.5 (c = 0.85, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 1.02–1.10 (m, 1 H, H-17), 1.27–1.37 (m, 1 H, H-18), 1.44–1.53 (m, 1 H, H-9), 1.84–2.23 (br m, 12 H, NMe₃, H-10, H-11, H-12, H-15, H-16, H-19), 2.97–3.05 (m, 2 H, H-7, H-8), 3.20–3.26 (m, 1 H, H-20), 3.44–3.52 (m, 2 H, H-13, H-14), 5.94 (dd, J = 7.0, 7.0 Hz, 1 H, H-21), 6.48 (d, J = 8.5 Hz, 1 H, H-5), 7.30–7.48 (m, 10 H, ArH), 8.14 (d, 1 H, H-6), 8.25 (s, 1 H, H-2). ¹³C NMR (100 MHz, CDCl₃): δ = 23.4, 25.6, 27.4, 40.3, 49.1, 49.7, 51.6, 57.9, 75.9 (q), 108.5, 117.7, 126.7, 126.8, 127.1, 130.5, 131.4, 148.9 (q), 149.6 (q), 150.0 (q), 170.3 (q). IR (neat): 2950, 2870, 2831, 2786, 1631, 1584, 1396, 1136, 976, 723, 706, 682 cm^–1. HRMS (ES): m/z [M + H]⁺ calcd for C₂₉H₃₅N₄O: 455.2811; found: 455.2818.

Supplementary Material

Supporting Information