Stereoselective Synthesis of Ketoses by Aldol Reaction Using Water-­Compatible Prolinamide Catalysts in Aqueous Media

Daisuke Miura; Takashi Fujimoto; Ayumi Tsutsui; Tomoya Machinami

doi:10.1055/s-0033-1339197

Synlett, Inhaltsverzeichnis

Synlett 2013; 24(12): 1501-1504
DOI: 10.1055/s-0033-1339197

letter

Stereoselective Synthesis of Ketoses by Aldol Reaction Using Water-Compatible Prolinamide Catalysts in Aqueous Media

Daisuke Miura

Department of Chemistry, College of Science and Technology, Meisei University, Hodokubo, Hino, Tokyo 191-8506, Japan Fax: +81(42)5917485 eMail: machinam@chem.meisei-u.ac.jp

,

Takashi Fujimoto

Department of Chemistry, College of Science and Technology, Meisei University, Hodokubo, Hino, Tokyo 191-8506, Japan Fax: +81(42)5917485 eMail: machinam@chem.meisei-u.ac.jp

,

Ayumi Tsutsui

Department of Chemistry, College of Science and Technology, Meisei University, Hodokubo, Hino, Tokyo 191-8506, Japan Fax: +81(42)5917485 eMail: machinam@chem.meisei-u.ac.jp

,

Tomoya Machinami*

Department of Chemistry, College of Science and Technology, Meisei University, Hodokubo, Hino, Tokyo 191-8506, Japan Fax: +81(42)5917485 eMail: machinam@chem.meisei-u.ac.jp

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Prolinamido-glycosides, water-compatible organocatalysts, are capable of catalyzing the stereoselective aldol reaction in aqueous media. The aldol reaction of 2,2-dimethyl-1,3-dioxan-5-one with aldehydo sugars in the isopropylidene form gave ketoses stereoselectively. The stereochemistry of these aldol reactions has been investigated in terms of the influence of conformational effects, and the results demonstrate that the configuration of the catalysts and the conformation of substrates are a determining factor in the stereochemical outcome of the reaction. Each of d-psicose and d-tagatose was selectively obtained from 2,3-O-isopropylidene-d-glyceraldehyde. Likewise, d-glycero-d-glucooctulose, whose structure was established by X-ray crystallography, was obtained from 2,3:4,5-di-O-isopropylidene-aldehydo-d-arabinose.

Key words

carbohydrates - aldol reaction - stereoselective synthesis - diastereoselectivity - catalysis

Volltext

Referenzen

References and Notes

1a Haines AH, Lamb AJ. Carbohydr. Res. 1999; 321: 197
1b Dondoni A, Merino P. J. Org. Chem. 1991; 56: 5294

2a List B, Lerner RA, Barbas CF. III. J. Am. Chem. Soc. 2000; 122: 2395
2b Sakthivel K, Not W, Bui T, Barbas CF. III. J. Am. Chem. Soc. 2001; 123: 5260
2c Notz W, Tanaka F, Barbas CF. III. Acc. Chem. Res. 2004; 37: 580
2d Córdva A, Notz W, Barbas CF. III. Chem. Commun. 2002; 3024
2e Nyberg AI, Usano A, Pihko PM. Synlett 2004; 1891

3a Suri JT, Pamachary DB, Barbas CF. III. Org. Lett. 2005; 7: 1383
3b Enders D, Grondal C. Angew. Chem. Int. Ed. 2005; 44: 1210
3c Kazmaier D. Angew. Chem. Int. Ed. 2005; 44: 2186
3d Grondal C, Enders D. Tetrahedron 2006; 62: 329
3e Ibrahem I, Córdva A. Tetrahedron. Lett. 2005; 46: 3363
3f Markert M, Mahrwald R. Chem. Eur. J. 2008; 14: 40
3g Northrup AB, MacMillan DW. C. J. Am. Chem. Soc. 2002; 124: 6798
3h Northrup AB, Mangion IK, Hettche F, MacMillan DW. C. Angew. Chem. Int. Ed. 2004; 43: 2152
3i Casas J, Engqvist M, Ibrahem I, Kaynak B, Córdva A. Angew. Chem. Int. Ed. 2005; 44: 1343
3j Palyman N, Niewczas I, Majewski M. Tetrahedron. Lett. 2007; 48: 9195
3k Niewczas I, Majewski M. Eur. J. Org. Chem. 2009; 33
3l Enders D, Narine AA. J. Org. Chem. 2008; 73: 7857

4a Dickerson TJ, Janda KD. J. Am. Chem. Soc. 2002; 124: 3220
4b Dickerson TJ, Lovell T, Meijler MM, Noodleman L, Janda KD. J. Org. Chem. 2004; 69: 6603
4c Rogers CJ, Dickerson TJ, Brogan AP, Janda KD. J. Org. Chem. 2005; 70: 3705

5a Pedatella S, De Nisco M, Mastroianni D, Naviglio D, Nucci A, Caputo R. Adv. Synth. Catal. 2011; 353: 1443
5b Burroughs L, Vale ME, Gilks JA, Forintos H, Hayes CJ, Clarke PA. Chem. Commun. 2010; 46: 4776
5c Scheffler U, Mahrwald R. J. Org. Chem. 2012; 77: 2313

6 Tsutsui A, Takeda H, Kimura M, Fujimoto T, Machinami T. Tetrahedron. Lett. 2007; 48: 5213

7a Chérest M, Felkin H, Prudent N. Tetrahedron. Lett. 1986; 69: 2199
7b Anh NT. Top. Curr. Chem. 1980; 88: 146

8 2,2-Dimethyl-1,3-dioxan-5-one (3) was synthesized by the method of Doyle and co-workers from tris(hydroxymethyl)aminomethane hydrochloride, see: Forbes DC, Ene DG, Doyle MP. Synthesis 1998; 879
9 2,3-O-Isopropylidene-d-glyceraldehyde (4) was prepared from d-mannitol as described by Schmid, see: Schmid CR, Bryant JD, Dowlatzedah M, Phillips JL, Prather DE, Schantz RD, Sear NL, Vianco CS. J. Org. Chem. 1991; 56: 4056
10 General Procedure for the Aldol Reaction of Prolinamido-glycosides Freshly distilled aldehydo sugar 4 or 9 (1.0 equiv) and 3 (1.1 equiv) were added to a stirred solution of the catalyst 1 or 2 (0.1 equiv) in H₂O (100 equiv), and the solution was stirred at r.t. After TLC indicated consumption of the starting materials, the solution was diluted with EtOAc, washed with H₂O, dried (Na₂SO₄), and concentrated to dryness. The residue was purified by column chromatography on silica gel with CHCl₃–EtOAc, to afford the uloses 5, 8, and 10. After completion of the reactions, the catalysts 1 and 2 could be separated by an extraction. Concentration of the aqueous layer, followed by recrystallization from 2-PrOH gave up to 75% recovery of the catalyst. Use of recovered 1 and 2 for the aldol reactions showed that the second aldol reactions were indistinguishable from the first aldol reactions in terms of yield and diastereoselectivity.
11 It is noteworthy that the foregoing reactions did not proceed at all when commercial 2,2-dimethyl-1,3-dioxan-5-one (3) and 2,3-O-isopropylidene-d-glyceraldehyde (4) were used, but when the reagents were freshly prepared, and distilled before use, the reactions progressed satisfactorily.

12a Majewski M, Nowak P. J. Org. Chem. 2000; 65: 5152
12b Majewski M, Nowak P. Synlett 1999; 1447
12c Grondal C, Enders D. Tetrahedron 2006; 62: 329
12d Suri JT, Mitsumori S, Albertshofer K, Tanaka F, Barbas CF. III. J. Org. Chem. 2006; 71: 3822

13 2,3:4,5-Di-O-isopropylidene-aldehydo-D-arabinose (9) was prepared from D-arabinose as described by Horton, see: Eitelman SJ, Horton D. Carbohydr. Res. 2006; 341: 2658
14 Compound 10: [α]_D ^26.1 +99° (c 1.0, CHCl₃); mp 94.0–95.5 °C. ¹H NMR (600 MHz, CDCl₃): δ = 1.34 (s, 3 H, IP), 1.36 (s, 3 H, IP), 1.42 (s, 3 H, IP), 1.43 (s, 3 H, IP), 1.44 (s, 3 H, IP), 1.48 (s, 3 H, IP), 3.18 (br s, 1 H, 4-OH), 3.99 (dd, 1 H, J _7,8 = 4.55 Hz, J _8a,8b = 8.51 Hz, H-8a), 4.01 (dd, 1 H, J _3,4 = 8.43 Hz, J _4,5 = 1.83 Hz, H4), 4.04–4.08 (m, 2 H, H-1a, H-7), 4.19 (t, 1 H, J _5,6 = 7.77 Hz, H-6), 4.19 (dd, 1 H, J _8a,8b = 8.51 Hz, H-8b), 4.19 (dd, 1 H, J _4,5 = 1.83 Hz, J _5,6 = 7.77 Hz, H-5), 4.30 (d, 1 H, J _1a,1b = 17.5 Hz, H-1b), 4.42 (d, 1 H, J _3,4 = 8.43 Hz, H-3). ¹³C NMR (150 MHz, CDCl₃): δ = 23.4 (IP), 23.6 (IP), 25.3 (IP), 26.6 (IP), 26.6 (IP), 27.0 (IP), 66.6 (C-1), 67.7 (C-8), 68.3 (C-4), 72.8 (C-3), 75.8 (C-6), 77.2 (C-7), 78.4 (C-5), 101.3 (IP), 109.1 (IP), 109.7 (IP), 211.5 (C-2). ESI-TOFMS: m/z calcd for [C₁₉H₃₂O₆ + Na]⁺: 379.02097; found: 379.02043. It crystallizes in the orthorhombic space group P2₁2₁2₁ with cell parameters a = 9.553(2) Å, b = 10.880(18) Å, c = 18.020(3) Å, and Z = 4, CCDC-931166.

15a Wolfrom ML, Thompson A. J. Am. Chem. Soc. 1946; 68: 1453
15b Richtmyer NK, Bodenheimer TS. J. Org. Chem. 1962; 27: 1892
15c Cieplak M, Ceborska M, Cmoch P, Jarosz S. Tetrahedron: Asymmetry 2012; 23: 1213

16 The aldol reactions of 2,3;4,5-di-O-isopropylidene-aldehydo-l-arabinose using either 1 nor 2 failed under the same conditions. Because of its extremely slow reaction rate when compared with its enantiomer, only trace amounts of aldol product were observed.

Conformational studies of the acyclic aldopentoses by NMR analysis were established by Horton and the term ‘sickle’ was introduced to designate the conformation generated from the extended, planar, zigzag form by rotation through 120° about an internal carbon–carbon bond. ₅ G ^– denotes the sickle conformation obtained by 120° clockwise rotation of the remote atom along the C-5–C-6 bond. For the sickle conformations, see:

17a Horton D. Pure Appl. Chem. 1975; 42: 301
17b Horton D, Wander JD. J. Org. Chem. 1974; 39: 1859
17c Horton D, Wander JD. Carbohydr. Res. 1969; 10: 279
17d Baker DC, Horton D. Carbohydr. Res. 1979; 69: 117
17e Horton D, Thomas S, Gallucci J. Carbohydr. Res. 2006; 341: 2211
17f Vejcik SM, Horton D. Carbohydr. Res. 2007; 342: 806
17g Horton D, Markovs RV. Carbohydr. Res. 1980; 80: 263
17h Horton D, Kokrady SS. Carbohydr. Res. 1980; 80: 364
17i Horton D, Wander JD. Carbohydr. Res. 1970; 13: 33
17j Horton D, Wander JD. Carbohydr. Res. 1970; 15: 271
17k Horton D, Wander JD. Adv. Carbohydr. Chem. Biochem. 1976; 32: 15

18 Compound 11: [α]_D ^25.2 +27° (c 1.0, CHCl₃). ¹H NMR (600 MHz, CHCl₃-d): δ = 1.33 (s, 3 H, IP), 1.37 (s, 3 H, IP), 1.41 (s, 3 H, IP), 1.42 (s, 3 H, IP), 1.46 (s, 3 H, IP), 1.47 (s, 3 H, IP), 2.11 (s, 3 H, Ac), 3.72 (t, 1 H, J _5,6 = 7.27 Hz, H-6), 3.95 (q, 1 H, J _7,8a = 7.27 Hz, J _8a,8b = 8.30 Hz, H-8a), 4.01 (d, 1 H, J _1a,1b = 17.3 Hz, H-1a), 4.10–4.13 (m, 2 H, H7, H-8b), 4.28 (d, 1 H, 1 H, J _1a,1b = 17.3 Hz, H-1b), 4.44 (dd, 1 H, J _4,5 = 2.56 Hz, J _5,6 = 7.27 Hz, H-5), δ 4.53 (d, 1 H, J _3,4 = 8.45 Hz, H-3), 5.34 (dd, 1 H, J _3,4 = 8.45 Hz, J _4,5 = 2.57 Hz, H-4). ¹³C NMR (150 MHz, CDCl₃): δ = 20.9 (Ac), 23.4 (IP), 24.2 (IP), 25.1 (IP), 26.2 (IP), 26.6 (IP), 27.3 (IP), 66.9 (C-1), 67.2 (C-8), 69.0 (C-4), 71.8 (C-3), 76.8 (C-7), 77.0 (C-6), 77.3 (C-5), 101.2 (IP), 109.7 (IP), 109.8 (IP), 170.0 (Ac), 206.7 (C-2). ESI-TOFMS: m/z calcd for [C₁₉H₃₀O₉ + Na]⁺: 425.17875; found: 425.17802.

Stereoselective Synthesis of Ketoses by Aldol Reaction Using Water-­Compatible Prolinamide Catalysts in Aqueous Media

Stereoselective Synthesis of Ketoses by Aldol Reaction Using Water-Compatible Prolinamide Catalysts in Aqueous Media