Organocatalytic Enantioselective Direct Aldol Reaction in Aqueous Media Catalyzed by a Bifunctional Diamine Catalyst

Abstract

Organocatalytic direct asymmetric anti-aldol reaction was developed in aqueous medium using a BINOL-derived diamine/protic acid bifunctional catalyst. The catalytic protocol could offer the opportunity to access anti-aldol products with high level of enantioselectivities with moderate diastereoselectivities.

aldol reaction - aqueous medium - organocatalyst - diamine - protic acid - enantioselectivity

References and Notes

1a Modern Aldol Reactions   Vol. 1:  Mahrwald R. Wiley-VCH; Weinheim: 2004. 

1b For metal-catalyzed reactions, see: Modern Aldol Reactions   Vol. 2:  Mahrwald R. Wiley-VCH; Weinheim: 2004. 

1c For a review, see: Casiraghi G. Zanardi F. Appendino G. Rassu G. Chem. Rev.  2000,  100:  1929 

2 List B. Lerner RA. Barbas CF. J. Am. Chem. Soc.  2000,  122:  2395 

3a Machajewski TD. Wong C.-H. Angew. Chem. Int. Ed.  2000,  39:  1352 

3b Gijsen HJM. Qiao L. Fitz W. Wong C.-H. Chem. Rev.  1996,  96:  443 

3c Wagner J. Lerner RA. Barbas CF. Science  1995,  270:  1797 

3d Dean SM. Greenberg WA. Wong C.-H. Adv. Synth. Catal.  2007,  349:  1308 

3e Li C. Feng X.-W. Wang N. Zhou Y.-J. Yu X.-Q. Green Chem.  2008,  10:  616 

4a Li H. Da C S. Xiao Y.-H. Li X. Su Y.-N. J. Org. Chem.  2008,  73:  7398 

4b Kantam ML. Ramani T. Chakrapani L. Kumar KV. Tetrahedron Lett.  2008,  49:  1498 

4c Paradowska J. Stodulski M. Mlynarski J. Adv. Synth. Catal.  2007,  349:  1041 

4d Evans DA. Downey CW. Hubbs JL. J. Am. Chem. Soc.  2003,  125:  8706 

4e Trost BM. Silcoff ER. Ito H. Org. Lett.  2001,  3:  2497 

4f Kumagai N. Matsunaga S. Yoshikawa N. Ohshima T. Shibasaki M. Org. Lett.  2001,  3:  1539 

For reviews on asymmetric organocatalytic aldol reactions, see:

5a Guillena G. Najera C. Ramon DJ. Tetrahedron: Asymmetry  2007,  18:  2249 

5b Tanaka F. Barbas CF. In Enantioselective Organocatalysis   Dalko PI. Wiley-VCH; Weinheim: 2007.  p.19 

5c Pellissier H. Tetrahedron  2007,  63:  9267 

5d Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev.  2007,  107:  5471 

6a Duarte FJS. Cabrita EJ. Frenking G. Santos AG. J. Org. Chem.  2010,  75:  2546 ; and references cited therein

6b Luo S. Qiao Y. Zhang L. Li J. Li X. Cheng J.-P. J. Org. Chem.  2009,  74:  9521 

6c Xiong Y. Wang F. Dong S. Liu X. Feng X. Synlett  2008,  73 

6d Luo S. Xu H. Zhang L. Li J. Cheng J.-P. Org. Lett.  2008,  10:  653 

6e Hayashi Y. Itoh T. Aratake S. Ishikawa H. Angew. Chem. Int. Ed.  2008,  47:  2082 

6f Xu X.-Y. Wang Y.-Z. Gong L.-Z. Org. Lett.  2007,  9:  4247 

For reviews, see:

6g Raj M. Singh VK. Chem. Commun.  2009,  6687 

6h List B. Acc. Chem. Res.  2004,  37:  548 

6i Notz W. Tanaka F. Barbas CF. Acc. Chem. Res.  2004,  37:  580 

6j Miller SJ. Acc. Chem. Res.  2004,  37:  601 

6k Saito S. Yamamoto H. Acc. Chem. Res.  2004,  37:  570 

7a Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 

For recent reports on organocatalytic aldol reactions, see:

7b Luo S. Xu H. Li J. Zhang L. Cheng J.-P.
J. Am. Chem. Soc.  2007,  129:  3074 

7c Ramasastry SSV. Zhang H. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2007,  129:  288 

7d Wang F. Xiong Y. Liu X. Feng X. Adv. Synth. Catal.  2007,  349:  2665 

7e Rodriguez B. Rantanen T. Bolm C. Angew. Chem. Int. Ed.  2006,  45:  6924 

7f D’Elia V. Zwicknagl H. Reiser O. Org. Lett.  2008,  73:  3262 

7g Kano T. Takai J. Tokuda O. Maruoka K. Angew. Chem. Int. Ed.  2005,  44:  3055 

8a Breslow R. Rizzo CJ. J. Am. Chem. Soc.  1991,  113:  4340 

8b Herrmann WA. Kohlpaintner CW. Angew. Chem., Int. Ed. Engl.  1997,  36:  1049 

For reviews, see:

8c Lindstrom UM. Chem. Rev.  2002,  102:  2751 

8d Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 

9a Sakthivel K. Notz W. Bui T. Barbas CF. J. Am. Chem. Soc.  2001,  123:  5260 

9b Torii H. Nakadai M. Ishihara K. Saito S. Yamamoto H. Angew. Chem. Int. Ed.  2004,  43:  1983 

9c Nyberg AI. Usanp A. Pihko PM. Synlett  2004,  1891 

9d Cordova A. Notz W. Barbas CF. Chem. Commun.  2002,  3024 

9e Darbre T. Machuqueiro M. Chem. Commun.  2003,  1090 

9f Tang Z. Yamg Z.-H. Cun L.-F. Gong L.-Z. Mi A.-Q. Jiang Y.-Z. Org. Lett.  2004,  6:  2285 

9g Chimni SS. Mahajan D. Suresh Babu VV. Tetrahedron Lett.  2005,  46:  5617 

10a Heine A. Desantis G. Luz JG. Mitchell M. Wong C.-H. Wilson IA. Science  2001,  294:  369 

10b Zhu X. Tanaka F. Hu Y. Heine A. Fuller R. Zhing G. Olson AJ. Lerner RA. Barbas CF. Wilson IA. J. Mol. Biol.  2004,  343:  1269 

11 Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 

12 Maya V. Singh VK. Org. Lett.  2009,  9:  1117 

13 For asymmetric aldol reaction using BINOL-derived primary amine, see: Liu Q.-Z. Wang X.-L. Luo S.-W. Zheng B.-L. Qin D.-B. Tetrahedron Lett.  2008,  49:  7434 

14a Raj M. Maya V. Ginotra SK. Singh VK. Org. Lett.  2006,  8:  4097 

14b Maya V. Raj M. Singh VK. Org. Lett.  2007,  9:  2593 

14c Gandhi S. Singh VK. J. Org. Chem.  2008,  73:  9411 

14d Raj M. Maya V. Singh VK. J. Org. Chem.  2009,  74:  4289 

15a Song L. Chen X. Zhang S. Zhang H. Li P. Luo G. Liu W. Duan W. Wang W. Org. Lett.  2008,  10:  5489 

15b Zhang H. Zhang S. Liu L. Luo G. Duan W. Wang W. J. Org. Chem.  2010,  75:  368 

For a diamine derived from trans-1,2-diaminocyclohexane and its application to direct asymmetric aldol reaction from our group, see:

16a Raj M. Parashari GS. Singh VK. Adv. Synth. Catal.  2009,  351:  1284 

16b Raj M. Veerasamy N. Singh VK. Tetrahedron Lett.  2010,  51:  2157 

17

General Procedure for the Direct Aldol Reaction with the Catalyst 3 in Brine: An aldehyde (0.5 mmol) was added to a mixture of ketone (2 mmol) and an organocatalyst 3 (10 mol%) with DNBSA (10 mol%) in brine (0.5 mL) at r.t. The reaction mixture was stirred and the progress of the reaction was monitored by TLC. After reaction was over (as indicated by TLC), the reaction mixture was diluted with EtOAc (2 mL). The organic layer was separated and dried over anhyd Na₂SO_4. It was purified over silica gel by column chromatography. The enantiomeric excess(ee) of the aldol product was determined by chiral HPLC analysis. The relative and absolute configurations of the products were determined by comparison with the known ^¹H NMR, chiral HPLC analysis, and optical rotation values.

18a Kumar A. Pawar SS. Tetrahedron  2003,  59:  5019 

18b Kleiner CM. Schreiner PR. Chem. Commun.  2006,  4315 

19a Nakadai M. Saito S. Yamamoto H. Tetrahedron  2002,  58:  8167 

19b Ishii T. Fiujioka S. Sekiguchi Y. Kotsuki H. J. Am. Chem. Soc.  2004,  126:  9558 

19c Seebach D. Golinski J. Helv. Chim. Acta  1981,  64:  1413 

20

Compound characterization data for selected compounds:
(2S,1′ R )-2-[Furan-2-yl(hydroxy)methyl]cyclohexan-1-one (4f): It was obtained in a maximum of 80% yield and 96% ee. The optical purity was determined by HPLC on chiralpak AD-H column (hexane-2-propanol, 90:10); flow rate 0.5 mL/min, 220 nm; t _{R ( major)} = 26.8 min, t _{R ( minor)} = 31.2 min; [α]^²5 _D +21 (c = 1.0, CHCl₃). ^¹H NMR (500 MHz, CDCl₃): δ = 1.23-1.35 (m, 1 H), 1.61-1.71 (m, 3 H), 1.83-1.85 (m, 1 H), 2.10-2.37 (m, 1 H), 2.38-2.49 (m, 2 H), 2.89-2.95 (m, 1 H), 3.89 (br s, 1 H), 4.83 (d, J = 8.6 Hz, 1 H), 6.27-6.34 (m, 2 H), 7.36-7.38 (m, 1 H). Anal. Calcd for C₁₁H₁₄O₃: C, 68.02; H, 7.27. Found: C, 68.09; H, 7.25.
(2S,1′ R )-2-[Hydroxy(naphthalene-2-yl)methyl]-cyclohexan-1-one (4g): It was obtained in a maximum of 88% yield and 96% ee. The optical purity was determined by HPLC on chiralpak AS-H column (hexane-2-propanol, 90:10); flow rate 0.5 mL/min; t _{R ( major)} = 26.6 min, t _{R ( minor)} = 30.8 min; [α]^²5 _D +5.8 (c = 1.3, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 1.25-1.35 (m, 2 H), 1.48-1.76 (m, 3 H), 2.04-2.09 (m, 1 H), 2.36-2.51 (m, 2 H), 2.69-2.75 (m, 1 H), 4.08 (br s, 1 H), 4.96 (d, J = 8.8 Hz, 1 H), 7.45-7.49 (m, 2 H), 7.71-7.89 (m, 5 H). Anal. Calcd for C₁₇H₁₈O₂: C, 80.28; H, 7.13. Found: C, 80.18; H, 7.11.
(2S,1′ R ) 3-[Hydroxy(phenyl)methyl]tetrahydrothio-pyran-4-one (5b): It was obtained in a maximum of 77% yield and 98% ee. The optical purity was determined by HPLC on chiralpak OD-H column (hexane-2-propanol, 98:2); flow rate 0.5 mL/min, t _{R ( major)} = 60.6 min, t _{R ( minor)} = 87.1 min; [α]^²5 _D +17.1 (c = 1.4, CHCl₃). ^¹H NMR (400 MHz, CDCl₃): δ = 2.48-2.60 (m, 2 H), 2.75-2.81 (m, 1 H), 2.83-2.88 (m, 1 H), 2.92-3.04 (m, 3 H), 3.42 (br s, 1 H), 4.97
(d, J = 8.8 Hz, 1 H), 7.26-7.39 (m, 5 H). Anal. Calcd for C₁₂H₁₄O₂S: C, 64.83; H, 6.35. Found: C, 64.89; H, 6.33.