The Organocatalytic Enantioselective Michael Addition of Aldehydes to Vinyl Sulfones in Water

Abstract

The first organocatalytic enantioselective Michael addition of aldehydes to vinyl sulfones in water was achieved using our rationally designed organocatalyst. The rigid nature of the tricycle with an inherent chiral pocket provides a well-organized chiral environment, which together with the hydrophobic pocket, enabled this elusive reaction to proceed smoothly in water.

Key words

organocatalytic - vinyl sulfone - Michael addition - aqueous reaction

Reference and Notes

• 1a Li CJ. Chan TH. Comprehensive Organic Reactions in Aqueous Media   Wiley; Hoboken: 2007. 
• 1b Grieco PA. Organic Synthesis in Water   Blackie; London: 1998. 
• 1c Joó F. Aqueous Organometallic Catalysis   Kluwer; Dordrecht: 2001. 
• 1d Cornils B. Herrmann WA. Aqueous Phase Organometallic Catalysis. Concepts and Applications   Wiley-VCH; Weinheim: 2004. 
• 1e Nakamura K. Matsuda T. In Organic Reactions in Water: Principles, Strategies and Applications   Lindström UM. Blackwell; Oxford: 2007.  p.301-349  
• 1f Breslow R. Acc. Chem. Res.  1991,  24:  159 
• 1g Li CJ. Chem. Rev.  1993,  93:  2023 
• 1h Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 
• 1i Li CJ. Chem. Rev.  2005,  105:  3095 
• 1j Li CJ. Chen L. Chem. Soc. Rev.  2006,  35:  68 
• 1k Herrerias CI. Yao X. Li Z. Li CJ. Chem. Rev.  2007,  107:  2546 
• 1l Dallinger D. Kappe CO. Chem. Rev.  2007,  107:  2563 
• 1m Minakata S. Komatsu M. Chem. Rev.  2009,  109:  711 
• 1n Chanda A. Fokin VV. Chem. Rev.  2009,  109:  725 
• For reviews on stereoselective organic reactions in aqueous media, see:
• 2a Sinou D. Adv. Synth. Catal.  2002,  344:  221 
• 2b Lindström UM. Chem. Rev.  2002,  102:  2751 
• 2c Manabe K. Kobayashi S. Chem. Eur. J.  2002,  8:  4094 
• 2d Dwars T. Oehme G. Adv. Synth. Catal.  2002,  344:  239 
• 2e Pan C. Wang Z. Coord. Chem. Rev.  2008,  252:  736 
• 2f Genêt JP. Darses S. Michelet V. Pure Appl. Chem.  2008,  80:  831 
• For reviews on organocatalysis in water, see:
• 3a Gruttadauria M. Giacalone F. Notoa R. Adv. Synth. Catal.  2009,  351:  33 
• For valuable discussions, see:
• 3b Brogan AP. Dickerson TJ. Janda KD. Angew. Chem. Int. Ed.  2006,  45:  8100 
• 3c Blackmond DG. Armstrong A. Coombe V. Wells A. Angew. Chem. Int. Ed.  2007,  46:  3798 
• 3d Hayashi Y. Angew. Chem. Int. Ed.  2006,  45:  8103 
• 3e Jung Y. Marcus RA. J. Am. Chem. Soc.  2007,  129:  5492 
• For leading references, see:
• 3f Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 
• 3g Hayashi Y. Sumiya T. Takahashi J. Gotoh H. Urushima T. Shoji M. Angew. Chem. Int. Ed.  2006,  45:  958 
• For descriptions of sulfone chemistry, see:
• 4a Simpkins NS. Sulfones in Organic Synthesis   Pergamon; Oxford: 1993. 
• 4b Toru T. Bolm C. Organosulfur Chemistry in Asymmetric Synthesis   Wiley-VCH; Weinheim: 2008. 
• For reviews, see:
• 4c El-Awa A. Noshi MN. Jourdin XM. Fuchs PL. Chem. Rev.  2009,  109:  2315 
• 4d Meadows DC. Gervay-Hague J. Med. Res. Rev.  2006,  26:  793 
• 4e Trost BM. Bull. Chem. Soc. Jpn.  1988,  61:  107 
• 4f Nájera C. Yus M. Tetrahedron  1999,  55:  10547 
• For asymmetric organocatalysis with sulfones, see:
• 4g Nielsen M. Jacobsen CB. Holub N. Paixão MW. Jørgensen KA. Angew. Chem. Int. Ed.  2010,  49:  2668 
• 4h Zhu Q. Lu Y. Aust. J. Chem.  2009,  62:  951 
• 5a Risaliti A. Fatutta S. Forchiassin M. Tetrahedron  1967,  23:  1451 
• 5b Forchiassin M. Risaliti A. Russo C. Calligaris M. Pitacco G. J. Chem. Soc., Perkin Trans. 1  1974,  660 
• 5c Benedetti F. Fabrissin S. Risaliti A. Tetrahedron  1984,  40:  977 
• 5d Modena G. Pasquato L. DeLucchi O. Tetrahedron Lett.  1984,  25:  3643 
• 6a Mossé S. Alexakis A. Org. Lett.  2005,  7:  4361 
• 6b Mossé S. Laars M. Kriis K. Kanger T. Alexakis A. Org. Lett.  2006,  8:  2559 
• 6c Quintard A. Bournaud C. Alexakis A. Chem. Eur. J.  2008,  14:  7504 
• 6d Mossé S. Alexakis A. Mareda J. Bollot G. Bernardinelli G. Filinchuk Y. Chem. Eur. J.  2009,  15:  3204 
• 7 Landa A. Maestro M. Masdeu C. Puente A. Vera S. Oiarbide M. Palomo C. Chem. Eur. J.  2009,  15:  1562 
• 8 Zhu Q. Lu Y. Org. Lett.  2008,  10:  4803 
• For Michael reactions of aldehydes to nitroolefins in water, see:
• 9a Mase N. Watanabe K. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  4966 
• 9b Zu L. Wang J. Li H. Wang W. Org. Lett.  2006,  8:  3077 
• 9c Zhu SL. Yu SY. Ma DW. Angew. Chem. Int. Ed.  2008,  47:  545 
• 9d Belot S. Massaro A. Tenti A. Mordini A. Alexakis A. Org. Lett.  2008,  10:  4557 
• 9e Zheng Z. Perkins BL. Ni B. J. Am. Chem. Soc.  2010,  132:  50 
• 9f Wu J. Ni B. Headley AD. Org. Lett.  2009,  11:  3354 
• 10a Xiao J. Loh TP. Synlett  2007,  815 
• 10b Xiao J. Loh TP. Org. Lett.  2009,  11:  2876 
• 10c Xiao J. Xu FX. Lu YP. Loh TP. Org. Lett.  2010,  12:  1220 
• 10d Xiao J. Wong ZZ. Lu YP. Loh TP. Adv. Synth. Catal.  2010,  352:  1107 
• 10e Loh TP. Chua GL. Chem. Commun.  2006,  2739 ; and references cited therein
• 11a Taniguchi M. Hino T. Tetrahedron  1981,  37:  1487 
• 11b Bourne GT. Crich D. Davies JW. Horwell DC. J. Chem. Soc., Perkin Trans. 1  1991,  1693 
• 11c Crich D. Banerjee A. Acc. Chem. Res.  2007,  40:  151 
• 11d Xiao J. Loh TP. Tetrahedron Lett.  2008,  49:  7184 

12

Typical Reaction Procedure
To a mixture of 1,1-bis(phenylsulfonyl)ethylene (31 mg, 0.1 mmol), catalyst I (2.8 mg, 0.01 mmol), and DMAP (1.2 mg, 0.01 mmol) in H₂O (0.5 mL) was added isoveraldehyde (34.4 mg, 0.4 mmol) and stirred vigorously for 12 h at r.t. Then MeOH (1 mL) was added and the mixture was cooled to 0 ˚C before NaBH₄ (8 mg, 0.2 mmol) was added. After stirring at 0 ˚C for 0.5 h, the mixture was extracted with EtOAc (3 × 5 mL). The combined organic layers were washed with brine (5 mL), dried over anhyd MgSO₄, and concentrated under reduced pressure. The desired products were purified with silica gel column chromatography (EtOAc-hexanes = 1:2). The ee was determined by HPLC with Chiralpak AS-H column at 220 nm (2-PrOH-hexane = 20:80), 0.5 mL/min, t _R(major) = 40.0 min, t _{R (}minor) = 47.0 min; [α]_D ^²0 +3.1 (c 2.3, CHCl₃, 589 nm); yellow light solid; R _f  = 0.15 (EtOAc-hexane = 1:2). ^¹H NMR (300 MHz, CDCl₃): δ = 7.98-7.93 (m, 4 H), 7.72-7.67 (m, 2 H), 7.59-7.54 (m, 4 H), 5.22 (dd, J = 3.3, 7.2 Hz, 1 H), 3.73 (dd, J = 3.3, 11.0 Hz, 1 H), 3.51 (dd, J = 7.9, 11.0 Hz, 1 H), 2.37-2.13 (m, 2 H), 1.78-1.57 (m, 3 H), 0.85 (d, J = 3.4 Hz, 3 H), 0.82 (d, J = 3.4 Hz, 3 H). ^¹³C NMR (75 Hz, CDCl₃): δ = 138.0, 137.7, 134.5, 129.7, 129.5, 129.1, 129.0, 81.6, 64.7, 44.4, 29.8, 26.1, 19.4, 19.2. HRMS (ESI-TOF): m/z calcd for C₁₉H₂₅SO₂: 333.1347 [M + H]⁺; found: 333.1342.