Oxo-Diels-Alder Reaction of Danishefsky’s Diene with Aldehydes, Catalyzed by Chiral Tridentate Chromium(III)-Schiff Base Complexes

Abstract

The enantioselective hetero-Diels-Alder reaction of Danishefsky’s diene with simple aromatic and aliphatic aldehydes is catalyzed by chiral tridentate Schiff base-chromium(III) complexes. In many cases, 2,3-dihydropyran-4-ones are obtained in good yields (up to 99%) and high enantioselectivities (up to 97%).

Key words

Diels-Alder reaction - tridentate Schiff base chromium(III) complexes - 2,3-dihydropyran-4-ones - Danishefsky’s diene - enantioselective catalysis

References and Notes

• For examples, see:
• 1a Noyori R. Asymmetric Catalysis in Organic Synthesis   Wiley; New York: 1994. 
• 1b Nicolaou KC. Sorensen EJ. Classics in Total Synthesis: Targets, Strategies, Methods   VCH; Weinheim: 1996. 
• For reviews, see:
• 2a Danishefsky SJ. DeNinno MP. Angew. Chem., Int. Ed. Engl.  1987,  26:  15 
• 2b Jørgensen KA. Angew. Chem. Int. Ed.  2000,  39:  3558 
• 2c Maruoka K. Catalysis in Asymmetric Synthesis   2nd ed.:  Ojima I. Wiley-VCH; New York: 2000.  Chap. 8A.
• 2d Pellissier H. Tetrahedron  2009,  65:  2839 
• 3a Kwiatkowski P. Asztemborska M. Caille J.-C. Jurczak J. Adv. Synth. Catal.  2003,  345:  506 
• 3b Malinowska M. Kwiatkowski P. Jurczak J. Tetrahedron Lett.  2004,  45:  7693 
• 3c Kwiatkowski P. Asztemborska M. Jurczak J. Tetrahedron: Asymmetry  2004,  15:  3189 
• 3d Kwiatkowski P. Asztemborska M. Jurczak J. Synlett  2004,  1755 
• 3e Kosior M. Kwiatkowski P. Asztemborska M. Jurczak J. Tetrahedron: Asymmetry  2005,  16:  2897 
• 3f Kwiatkowski P. Chaadaj W. Malinowska M. Asztemborska M. Jurczak J. Tetrahedron: Asymmetry  2005,  16:  2959 
• 3g Chaadaj W. Kwiatkowski P. Jurczak J. Synlett  2006,  3263 
• 4 Chaadaj W. Kwiatkowski P. Jurczak J. Tetrahedron Lett.  2008,  49:  6810 
• 5a Dossetter AG. Jamison TF. Jacobsen EN. Angew. Chem. Int. Ed.  1999,  38:  2398 ; Angew. Chem. 1999, 111, 2549
• 5b Thompson CF. Jamison TF. Jacobsen EN. J. Am. Chem. Soc.  2000,  122:  10482 
• 5c Chavez DE. Jacobsen EN. Angew. Chem. Int. Ed.  2001,  40:  3667 
• 5d Paterson I. De Savi C. Tudge M. Org. Lett.  2001,  3:  3149 
• 5e Liu P. Jacobsen EN. J. Am. Chem. Soc.  2001,  123:  10772 
• 5f Chavez DE. Jacobsen EN. Angew. Chem. Int. Ed.  2001,  40:  3667 
• 5g Thompson CF. Jamison TF. Jacobsen EN. J. Am. Chem. Soc.  2001,  123:  9974 
• 5h Paterson I. Tudge M. Angew. Chem. Int. Ed.  2003,  42:  343 
• 5i Paterson I. Tudge M. Tetrahedron  2003,  59:  6833 
• 5j Paterson I. Luckhurst CA. Tetrahedron Lett.  2003,  44:  3749 
• 5k Louis I. Hungerford NL. Humphries EJ. McLeod MD. Org. Lett.  2006,  8:  1117 
• 5l Bonazzi S. Güttinger S. Zemp I. Kutay U. Gademann K. Angew. Chem. Int. Ed.  2007,  46:  8707 
• 5m Gosh AK. Gong G. Org. Lett.  2007,  9:  1437 
• 6a Cox JM. Rainier JD. Org. Lett.  2001,  3:  2919 
• 6b Smith AB. Fox RJ. Vanecko JA. Org. Lett.  2005,  7:  3099 
• 6c Sanz MA. Voigt T. Waldmann H. Adv. Synth. Catal.  2006,  348:  1511 
• 6d Lucas BS. Luther LM. Burke SD. J. Org. Chem.  2005,  70:  3757 
• 6e Majumder U. Cox JM. Johnson HWB. Rainier JD. Chem. Eur. J.  2006,  12:  1736 
• 7 Joly GD. Jacobsen EN. Org. Lett.  2002,  4:  1795 
• 8a Bhattacharjee A. De Brabander JK. Tetrahedron Lett.  2000,  41:  8069 
• 8b Paterson I. Steven A. Luckhurst CA. Org. Biomol. Chem.  2004,  2:  3026 
• 8c Smith AB. Razler TM. Ciavarri JP. Hirose T. Ishikawa T. Meis RM. J. Org. Chem.  2008,  73:  1192 
• 10 Danishefsky SJ. Larson E. Askin D. Kato N. J. Am. Chem. Soc.  1985,  107:  1246 
• 12 Guillaneux D. Zhao SH. Samuel O. Rainford D. Kagan HB. J. Am. Chem. Soc.  1994,  116:  9430 

9

Typical procedure: Catalyst 2b (5.4 mg, 1 mol%) and a magnetic stirring bar was placed in a Schlenk tube and the atmosphere was replaced with argon. Under a gentle stream of argon, EtOAc (0.5 mL) was added. After dissolving the catalyst, the mixture was heated at 50 ˚C for 30 min, followed by addition of a freshly distilled aldehyde (4; 0.5 mmol) and then Danishefsky’s diene (3; 110 µL, 0.6 mmol) under a gentle stream of argon. The reaction was carried out at 50 ˚C for 12 h. After that time, the reaction mixture was cooled to r.t. and quenched with TFA (3 drops). After 30 min, the reaction mixture was diluted with CH₂Cl₂ and extracted with sat. aq K₂CO₃, H₂O, and brine. The organic phase was concentrated and purified by chromatography over silica gel.

11

^¹H NMR (200 MHz, CDCl₃): δ = 2.6 (dd, J = 8.6, 3.8 Hz, 2 H), 2.75 (dd, J = 15, 3 Hz, 2 H), 3.6 (s, 3 H), 4.7 (m, 1 H), 4.7 (dd, J = 5.6, 2.2 Hz, 1 H), 7.4 (m, 5 H); ^¹³C NMR (50 MHz, CDCl₃): δ = 47.6, 48.6, 56.6, 73.2, 101.2, 125.7, 128.1, 128.6, 140.0, 204.9; IR: 2848, 1722, 1460, 1391, 1276, 1135, 1045, 762, 700, 460 cm^-¹; MS: m/z [M + Na + MeOH]⁺ calcd: 261.11094; found: 261.10973 (in the presence of EtOH instead of MeOH, the observed ion was [M + Na + EtOH]⁺: calcd 275.12403; found: 275.12538); Anal. Calcd for C₁₂H₁₄O₃: C, 69.88; H, 6.84; O, 23.27. Found: C, 69.93; H, 6.91; O, 23.16.