Highly Enantio- and Diastereoselective l-Proline Derived Acetylglucose Amide Catalyzed Aldol Reaction of Ketones to Aldehydes under Solvent-Free Conditions

Xiaoyu Han; Yongjiang Wang; Xikun Gai; Xiaofei Zeng

doi:10.1055/s-0035-1560701

Synlett, Table of Contents

Synlett 2015; 26(20): 2858-2862
DOI: 10.1055/s-0035-1560701

letter

Highly Enantio- and Diastereoselective l-Proline Derived Acetylglucose Amide Catalyzed Aldol Reaction of Ketones to Aldehydes under Solvent-Free Conditions

Xiaoyu Han*

^aZhejiang Provincial Key Laboratory for Chemical &Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, No. 318 Liuhe Road, Hangzhou, 310023, P. R. of China Email: chemhanxy@zust.edu.cn

,

Yongjiang Wang

^aZhejiang Provincial Key Laboratory for Chemical &Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, No. 318 Liuhe Road, Hangzhou, 310023, P. R. of China Email: chemhanxy@zust.edu.cn

,

Xikun Gai

^aZhejiang Provincial Key Laboratory for Chemical &Biological Processing Technology of Farm Products, School of Biological and Chemical Engineering, Zhejiang University of Science and Technology, No. 318 Liuhe Road, Hangzhou, 310023, P. R. of China Email: chemhanxy@zust.edu.cn

,

Xiaofei Zeng*

^bCollege of Material, Chemistry and Chemical Engineering, Hangzhou Normal University, Hangzhou 310036, P. R. of China Email: chemzxf@hznu.edu.cn

› Author Affiliations

Abstract

All articles of this category

Abstract

A novel organocatalyst was developed from d-glucosamine and l-proline, which was shown to catalyze the direct aldol reaction of ketones with aldehydes in a highly diastereoselective and enantioselective manner under solvent-free conditions. The presence of 10 mol% catalyst could promote the reaction effectively, affording the desired aldol products in high yields (70–99%) and excellent selectivities (up to >99:1 dr and up to >99% ee).

Key words

organocatalyst - stereoselectivity - enantioselectivity - aldol reaction - solvent-free

Full Text

References

References and Notes

1a Trost BM, Brindle CS. Chem. Soc. Rev. 2010; 39: 1600
1b Bisai V, Bisai A, Singh VK. Tetrahedron 2012; 68: 4541
1c Mlynarski J, Gut B. Chem. Soc. Rev. 2012; 41: 587
1d Casiraghi G, Zanardi F, Appendino G, Rassu G. Chem. Rev. 2000; 100: 1929
1e Machajewski TD, Wong CH. Angew. Chem. Int. Ed. 2000; 39: 1352
1f Mukaiyama T. Angew. Chem. Int. Ed. 2004; 43: 5590
1g Zhang H, Zhang S, Liu L, Luo G, Duan W, Wang W. J. Org. Chem. 2010; 75: 368
1h Hara N, Tamura R, Funahashi Y, Nakamura S. Org. Lett. 2011; 13: 1662

For reviews, see:

2a Gröger H, Vogl EM, Shibasaki M. Chem. Eur. J. 1998; 4: 1137
2b Nelson SG. Tetrahedron: Asymmetry 1998; 9: 357
2c Carreira E. M. In Comprehensive Asymmetric Catalysis, Vol. 3; Jacobsen, E. N.; Platz, A.; Yamamoto, H.; Eds.; Springer: Heidelberg, 1999, 997.
2d Mahrwald R. Chem. Rev. 1999; 99: 1095
2e Machajewski TD, Wong C.-H. Angew. Chem. Int. Ed. 2000; 39: 1352 ; Angew. Chem. 2000, 112, 1406
2f Johnson JS, Evans DA. Acc. Chem. Res. 2000; 33: 325
2g Denmark SE, Stavenger RA. Acc. Chem. Res. 2000; 33: 432
2h Palomo C, Oiarbide M, García JM. Chem. Soc. Rev. 2004; 33: 65
2i Modern Aldol Reaction . Vol. 1 and 2. Mahrwald R. Wiley-VCH; Weinheim: 2004

3a List B, Lerner RA, Barbas CF. III. J. Am. Chem. Soc. 2000; 122: 2395
3b Notz W, List B. J. Am. Chem. Soc. 2000; 122: 7386
3c Bahmanyar S, Houk KN, Martin HJ, List B. J. Am. Chem. Soc. 2003; 125: 2475
3d Sakthivel K, Notz W, Bui T, Barbas CF. III. J. Am. Chem. Soc. 2001; 123: 5260
3e Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007; 107: 5471

For selected reviews on the aldol and other reactions using asymmetric organocatalysis, see:

4a Guillena G, Najera C, Ramón DJ. Tetrahedron: Asymmetry 2007; 18: 2249
4b Seayad J, List B. Org. Biomol. Chem. 2005; 3: 719
4c Notz W, Tanaka F, Barbas CF. III. Acc. Chem. Res. 2004; 37: 580
4d List B. Acc. Chem. Res. 2004; 37: 548
4e Allemann C, Gordillo R, Clemente FR, Cheong PH.-Y, Houk KN. Acc. Chem. Res. 2004; 37: 558
4f Dondoni A, Massi A. Angew. Chem. Int. Ed. 2008; 47: 4638
4g Trost BM, Brindle CS. Chem. Soc. Rev. 2010; 39: 1600
4h Bisai V, Bisai A, Singh VK. Tetrahedron 2012; 68: 4541
4i Modern Methods in Stereoselective Aldol Reactions. Mahrwald R. Wiley-VCH; Weinheim: 2013
4j Hernández JG, Juaristi E. Chem. Commun. 2012; 48: 5396
4k Bisai V, Bisai A, Singh VK. Tetrahedron 2012; 68: 4541

5a Agarwal J, Peddinti RK. Eur. J. Org. Chem. 2012; 6390
5b Fotaras S, Kokotos CG, Kokotos G. Org. Biomol. Chem. 2012; 10: 5613
5c Pedrosa R, Andrés JM, Gamarra A, Manzano R, Pérez-López C. Tetrahedron 2013; 69: 10811
5d Revelou P, Kokotos CG, Moutevelis-Minakakis P. Tetrahedron 2012; 68: 8732
5e Tanimura Y, Yasunaga K, Ishimaru K. Eur. J. Org. Chem. 2013; 6535
5f Gioia C, Ricci A, Bernardi L, Bourahla K, Tanchoux N, Robitzer M, Quignard F. Eur. J. Org. Chem. 2013; 588
5g Hayashi Y, Aratake S, Okano T, Takahashi J, Sumiya T, Shoji M. Angew. Chem. Int. Ed. 2006; 45: 5527
5h Huang JM, Zhang XT, Armstrong DW. Angew. Chem. Int. Ed. 2007; 46: 9073
5i Siyutkin DE, Kucherenko AS, Struchkova MI, Zlotin SG. Tetrahedron Lett. 2008; 49: 1212
5j Zhang SP, Fu XK, Fu SD, Pan JF. Catal. Commun. 2008; 10: 401
5k Chimni SS, Singh S, Mahajan D. Tetrahedron: Asymmetry 2008; 19: 2276
5l Zhang SP, Fu XK, Fu SD. Tetrahedron Lett. 2009; 50: 1173
5m Sagamanova IK, Sayalero S, Martínez-Arranz S, Albéniz AC, Pericàs MA. Catal. Sci. Technol. 2015; 5: 754
5n Kumar TP, Vavle NC, Patro V, Haribabu K. Tetrahedron: Asymmetry 2014; 25: 457
5o Guan Z, Luo Y, Zhang B.-Q, Heinen K, Yang DC, He Y.-H. Tetrahedron: Asymmetry 2014; 25: 802
5p Liu K, Zhang G. Tetrahedron Lett. 2015; 56: 243
5q Jiang Z, Liang Z, Wu X, Lu Y. Chem. Commun. 2006; 2801
5r Wu X, Jiang Z, Shen H.-M, Lu Y. Adv. Synth. Catal. 2007; 349: 812
5s Hernández JG, Juaristi E. Tetrahedron 2011; 67: 6953

For examples of direct aldol reactions using organocatalysts under solvent-free conditions, see:

6a Hayashi Y, Aratake S, Itoh T, Okano T, Sumiya T, Shoji M. Chem. Commun. 2007; 957
6b Guillena G, Hita MC, Nájera C, Viózquez SF. Tetrahedron: Asymmetry 2007; 18: 2300
6c Rodríguez B, Bruckmann A, Bolm C. Chem. Eur. J. 2007; 13: 4710
6d Yan J, Wang L. Synthesis 2008; 2065
6e Almaşi D, Alonso DA, Nájera C. Adv. Synth. Catal. 2008; 350: 2467
6f Guillena G, Nájera C, Viózquez SF. Synlett 2008; 3031
6g Guillena G, Hita MC, Nájera C, Viózquez SF. J. Org. Chem. 2008; 73: 5933
6h Almaşi D, Alonso DA, Nájera C. Adv. Synth. Catal. 2009; 351: 1123
6i Worch C, Bolm C. Synlett 2009; 2425
6j Bradshaw B, Etxebarría-Jardi G, Bonjoch J, Viózquez SF, Guillena G, Nájera C. Adv. Synth. Catal. 2009; 351: 2482
6k Agarwal J, Peddinti RK. Tetrahedron: Asymmetry 2010; 21: 1906
6l Hernández JG, Juaristi E. J. Org. Chem. 2011; 76: 1464
6m Machuca E, Rojas Y, Juaristi E. Asian J. Org. Chem. 2015; 4: 46
6n Hernández JG, García-López V, Juaristi E. Tetrahedron 2012; 68: 92
6o Machuca E, Juaristi E. Tetrahedron Lett. 2015; 56: 1144
6p Martínez-Castañeda Á, Poladura B, Rodríguez-Solla H, Concellón C, Amo V. Org. Lett. 2011; 13: 3032
6q Martínez-Castañeda Á, Poladura B, Rodríguez-Solla H, Concellón C, Amo V. Chem. Eur. J. 2012; 18: 5188
6r Zhang F, Li C, Qi C. Tetrahedron: Asymmetry 2013; 24: 380
6s Bañón-Caballero A, Guillena G, Nájera C, Faggi E, Sebastián RM, Vallribera A. Tetrahedron 2013; 69: 1307
6t Wan W, Gao W, Ma G, Ma L, Wang F, Wang J, Jiang H, Zhu S, Hao J. RSC Adv. 2014; 4: 26563

7a Dwek RA. Chem. Rev. 1996; 96: 683
7b Zachara NE, Hart GW. Chem. Rev. 2002; 102: 431
7c D’Almeida A, Ionata M, Tran V, Tellier C, Dion M, Rabiller C. Tetrahedron: Asymmetry 2009; 20: 1243
7d Frontana-Uribe BA, Escárcega-Bobadilla MV, Juárez-Lagunas J, Toscano RA, García de la Mora GA, Salmón M. Synthesis 2009; 980
7e Ran C.-Z, Pantazopoulos P, Medarova Z, Moore A. Angew. Chem. Int. Ed. 2007; 46: 8998
7f Cassaro RF, de Oliveira LC, Gariani RA, do Nascimento CA. O, Bazito RC. Green Process Synth. 2013; 2: 43

8a Tsutsui A, Takeda H, Kimura M, Fjimoto T, Machinami T. Tetrahedron Lett. 2007; 48: 5213
8b Miura D, Fujimoto T, Tsutsui A, Machinami T. Synlett 2013; 24: 1501

9 Catalytic Asymmetric Aldol Reaction; Typical Procedure: Cyclohexanone (0.2 mmol, 2.0 equiv), aldehyde (0.1 mmol, 1.0 equiv), and catalyst 1 (0.01 mmol, 10 mol%) were mixed together at room temperature. The mixture was stirred at room temperature until the aldehyde was consumed (reaction monitored by TLC). The mixture was diluted with CH₂Cl₂ (0.5 mL), and then purified directly by column chromatography on silica gel to give the desired optically active aldol product. Analytical data of compound 4b are given as a representative compound (see the Supporting Information data on all products). Yield: 0.0241 g (96%); yellow solid; [α] _d ²⁰ –29 (c = 1.0, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 8.22–8.16 (m, 2 H), 7.68 (d, J = 7.4 Hz, 1 H), 7.55 (d, J = 7.4 Hz, 1 H), 4.91 (dd, J = 2.7, 8.2 Hz, 1 H), 4.15 (d, J = 2.8 Hz, 1 H), 2.66–2.62 (m, 1 H), 2.53–2.38 (m, 2 H), 2.14–2.11 (m, 1 H), 1.86–1.57 (m, 3 H), 1.42–1.38 (m, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 215.0, 148.3, 143.2, 133.2, 129.3, 122.9, 122.0, 74.0, 57.1, 42.7, 30.7, 27.6, 24.6. HRMS: m/z [M⁺] calcd for C₁₃H₁₅NO₄: 249.1001; found: 249.1099.

Supplementary Material

Supporting Information