Catalytic Asymmetric Ring-Opening of σ-Symmetric Cyclic Carbonates with Chiral Brønsted Acid Catalysts

Shigeki Sano; Takeshi Tsumura; Masashi Horibe; Michiyasu Nakao

doi:10.1055/s-0033-1339845

Synlett, Table of Contents

Synlett 2013; 24(17): 2302-2304
DOI: 10.1055/s-0033-1339845

letter

Catalytic Asymmetric Ring-Opening of σ-Symmetric Cyclic Carbonates with Chiral Brønsted Acid Catalysts

Shigeki Sano*

Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan Fax: +81(88)6339503 Email: ssano@tokushima-u.ac.jp

,

Takeshi Tsumura

Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan Fax: +81(88)6339503 Email: ssano@tokushima-u.ac.jp

,

Masashi Horibe

Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan Fax: +81(88)6339503 Email: ssano@tokushima-u.ac.jp

,

Michiyasu Nakao

Graduate School of Pharmaceutical Sciences, The University of Tokushima, Sho-machi, Tokushima 770-8505, Japan Fax: +81(88)6339503 Email: ssano@tokushima-u.ac.jp

› Author Affiliations

Abstract

All articles of this category

Abstract

Enantioselective ring-opening of σ-symmetric six-membered cyclic carbonates with benzyl alcohol catalyzed by BINOL-based chiral phosphoric acids was achieved in up to 81% enantiomeric excess at 5 mol% catalyst loading.

Key words

ring opening - cyclic carbonate - Brønsted acid - phosphoric acid - asymmetric synthesis - organocatalyst

Full Text

References

References and Notes

For selected reviews on desymmetrization in organic synthesis, see:

1a Gracía-Urdiales E, Alfonso I, Gotor V. Chem. Rev. 2005; 105: 313
1b Nakahara K, Fujioka H. Symmetry 2010; 2: 437
1c Gracía-Urdiales E, Alfonso I, Gotor V. Chem. Rev. 2011; 111: PR110

2a Tamai S, Miyauchi S, Morizane C, Miyagi K, Shimizu H, Kume M, Sano S, Shiro M, Nagao Y. Chem. Lett. 1994; 23: 2381
2b Sano S, Hayashi K, Miwa T, Ishii T, Fujii M, Mima H, Nagao Y. Tetrahedron Lett. 1998; 39: 5571
2c Sano S, Miwa T, Hayashi K, Nozaki K, Ozaki Y, Nagao Y. Tetrahedron Lett. 2001; 42: 4029

3a Honjo T, Sano S, Shiro M, Nagao Y. Angew. Chem. Int. Ed. 2005; 44: 5838
3b Honjo T, Tsumura T, Sano S, Nagao Y, Yamaguchi K, Sei Y. Synlett 2009; 3279

4a Sano S, Nakao M, Takeyasu M, Honjo T, Nagao Y. Lett. Org. Chem. 2006; 3: 764
4b Honjo T, Nakao M, Sano S, Shiro M, Yamaguchi K, Sei Y, Nagao Y. Org. Lett. 2007; 9: 509
4c Sano S, Nakao M, Takeyasu M, Yamamoto C, Kitaike S, Yoshioka Y, Nagao Y. Open Org. Chem. J. 2009; 3: 22
4d Sano S, Tsumura T, Tanimoto N, Honjo T, Nakao M, Nagao Y. Synlett 2010; 256

For selected reviews on asymmetric organocatalysis, see:

5a Schreiner PR. Chem. Soc. Rev. 2003; 32: 289
5b Notz W, Tanaka F, Barbas CF. III. Acc. Chem. Res. 2004; 37: 580
5c List B. Chem. Rev. 2007; 107: 5413
5d Jaroch S, Weinmann H, Zeitler K. ChemMedChem 2007; 2: 1261
5e MacMillan DW. C. Nature 2008; 455: 304
5f Palomo C, Oiarbide M, López R. Chem. Soc. Rev. 2009; 38: 632
5g Pellissier H. Adv. Synth. Catal. 2011; 353: 659
5h Alemán J, Cabrera S. Chem. Soc. Rev. 2013; 42: 774

For selected reviews on chiral Brønsted acid catalysis, see:

6a Akiyama T, Itoh J, Fuchibe K. Adv. Synth. Catal. 2006; 348: 999
6b Taylor MS, Jacobsen EN. Angew. Chem. Int. Ed. 2006; 45: 1520
6c Rueping M, Koenigs RM, Atodiresei I. Chem. Eur. J. 2010; 16: 9350
6d Zamfir A, Schenker S, Freund M, Tsogoeva SB. Org. Biomol. Chem. 2010; 8: 5262
6e Parra A, Reboredo S, Castro AM. M, Alemán J. Org. Biomol. Chem. 2012; 10: 5001

7 Nagorny P, Sun Z, Winschel GA. Synlett 2013; 24: 661

For selected reviews on cyclic carbonates, see:

8a Suriano F, Coulembier O, Hedrick JL, Dubois P. Polym. Chem. 2011; 2: 528
8b Tempelaar S, Mespouille L, Coulembier O, Dubois P, Dove AP. Chem. Soc. Rev. 2013; 42: 1312

9 Matsumoto K, Sato Y, Shimojo M, Hatanaka M. Tetrahedron: Asymmetry 2000; 11: 1965
10 Al-Azemi TF, Dib HH, Al-Awadi NA, El-Dusouqui OM. E. Tetrahedron 2008; 64: 4126

For ring-opening of aziridines catalyzed by BINOL-based phosphoric acids, see:

11a Rowland EB, Rowland GB, Rivera-Otero E, Antilla JC. J. Am. Chem. Soc. 2007; 129: 12084
11b Larson SE, Baso JC, Li G, Antilla JC. Org. Lett. 2009; 11: 5186

Chiral Brønsted acids 3a–e, 3g, 3h, and 3j–l were prepared according to previously reported methods. Catalysts 3f and 3i were purchased from a commercial source.

12a For 3a, 3d, and 3g, see: Yamanaka M, Itoh J, Fuchibe K, Akiyama T. J. Am. Chem. Soc. 2007; 129: 6756
12b For 3b, see: Hatano M, Ikeno T, Matsumura T, Torii S, Ishihara K. Adv. Synth. Catal. 2008; 350: 1776
12c For 3c, see: Zhang Y.-L, Zhang F, Tang W.-J, Wu Q.-L, Fan Q.-H. Synlett 2006; 1250
12d For 3e, 3j, 3k, and 3l, see: Storer RI, Carrera DE, Ni Y, MacMillan DW. C. J. Am. Chem. Soc. 2006; 128: 84
12e For 3h, see: Akiyama T, Morita H, Itoh J, Fuchibe K. Org. Lett. 2005; 7: 2583

13a Akiyama T, Itoh J, Yokota K, Fuchibe K. Angew. Chem. Int. Ed. 2004; 43: 1566
13b Uraguchi D, Terada M. J. Am. Chem. Soc. 2004; 126: 5356
13c Akiyama T. Chem. Rev. 2007; 107: 5744

14 Catalytic Asymmetric Ring-Opening of Cyclic Carbonates; Typical Procedure: To a solution of cyclic carbonate 1c (33.9 mg, 0.1 mmol) and chiral Brønsted acid catalyst 3k (4.1 mg, 0.005 mmol) in CH₂Cl₂ (1 mL), was added BnOH (52 μL, 0.5 mmol) at r.t. After stirring at r.t. for 20 h, the reaction mixture was treated with sat. aq NaHCO₃ (2 mL) followed by extraction with CHCl₃ (24 mL). The extract was dried over anhydrous MgSO₄, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (n-hexane–EtOAc, 1:1) to afford acylic carbonate 2c (41.8 mg, 94% yield, 81% ee) as a white solid. The ee of 2c was determined by HPLC analysis on a Chiralpak AD-H column (n-hexane–EtOH, 1:1; flow rate = 1 mL/min; detection = 254 nm). The retention times were 9.2 min (minor product) and 11.9 min (major product).
15 Spectroscopic Data of 2c: White solid; mp 81.0–82.5 °C; [α]_D ²⁷ –4.3 (c 1.02, CHCl₃). ¹H NMR (500 MHz, CDCl₃): δ = 2.20 (br. s, 1 H), 3.60–3.78 (m, 2 H), 3.91–4.01 (m, 1 H), 4.20 (t, J = 6.7 Hz, 1 H), 4.23–4.36 (m, 2 H), 4.42 (d, J = 6.4 Hz, 2 H), 5.15–5.23 (m, 1 H), 5.17 (s, 2 H), 7.31 (dt, J = 1.1, 7.5 Hz, 2 H), 7.33–7.42 (m, 7 H), 7.57 (d, J = 7.5 Hz, 2 H), 7.76 (d, J = 7.6 Hz, 2 H). ¹³C NMR (125 MHz, CDCl₃): δ = 47.2, 51.5, 61.5, 66.3, 67.0, 70.2, 120.0, 125.0, 127.1, 127.7, 128.5, 128.7, 128.8, 134.8, 141.3, 143.78, 143.81, 155.3, 156.2. IR (KBr): 3322, 2960, 1744, 1692, 1538, 1270 cm^–1. MS (ESI): m/z [M⁺ + Na] calcd for C₂₆H₂₅NNaO₆: 470.1580; found: 470.1583.