Carbonyl umpolung reactivity of enals: NHC-catalyzed synthesis of aldol products via epoxide ring opening

Synlett

Volumn , Issue 2, 2010, Pages 240-246

  Yadav, Lal Dhar S ^a   Singh, Santosh ^a   Rai, Vijai K ^a,b  

^a UNIVERSITY OF ALLAHABAD   (India)

^b SHRI MATA VAISHNO DEVI UNIVERSITY   (India)

Author keywords

Aldols; Enals; Epoxides; N heterocyclic carbenes; Tetrahydropyran 4 ones; Umpolung

Indexed keywords

CARBENE; CARBONYL DERIVATIVE; ELECTROPHILE; EPOXIDE; NUCLEOPHILE; TETRAHYDROPYRAN 4 ONE DERIVATIVE; TETRAHYDROPYRAN DERIVATIVE; UNCLASSIFIED DRUG;

ALDOL REACTION; ARTICLE; CYCLIZATION; ONE POT SYNTHESIS; RING OPENING;

EID: 75649134925     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-0029-1218563     Document Type: Article

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51. 6: C, 59.65; H, 4.12; N, 8.18. Found: C, 59.92; H, 3.89; N, 7.91.
52. General Procedure for the Synthesis of Aldol Products 4 A flame-dried round-bottom flask was charged with benzimidazolium salt 3a (0.3 mmol). a,b-unsaturated aldehyde 1 (1.0 mmol), epoxide 2 (1.5 mmol), and THF t-BuOH (10:1, 5 mL) under positive pressure of nitrogen followed by addition of DBU (0.3 mmol) with a syringe. The resulting yellow-orange solution was stirred for 1518 h atr.t. (Table 2). After completion of the reaction (monitored by TLC), the reaction mixture was concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel using hexaneEtOAc (10:1) as eluent to afford analytically pure 4. Characterization Data of Representative Compounds 4 Compound 4c: IR (KBr): nmax = 3439, 3021, 2929, 1676, 1627, 1608, 1585, 1453, 1347 cm1. 1H NMR (400 MHz, CDCl3): d = 3.09 (dd, 1 H, J = 17.3, 9.1 Hz, a-Ha), 3.17 (dd, 1 H, J = 17.3, 3.5 Hz, a-Hb), 3.69 (d, 1 H J = 2.9 Hz, OH), 5.20 (ddd, 1 H, J = 9.1, 3.5, 2.9 Hz, b-H), 6.73 (d, 1 H, J = 16.5 Hz, a-H), 7.537.41 (m, 5 Harom, Ph), 7.59 (d, 2 Harom, J = 8.7 Hz, 4-O2NC6H4), 7.65 (d, 1 H, J = 16.5 Hz, b- H), 8.27 (d, 2 Harom, J = 8.7 Hz, 4-O2NC6H4). 13C NMR (100 MHz, CDCl3TMS): d = 48.6, 69.5, 122.3, 126.5, 127.8, 128.5, 129.1, 129.9, 134.2, 141.3, 144.1, 147.9, 199.7. MS (EI): m/z = 297 [M+]. Anal. Calcd for C17H15NO4: C, 68.68; H, 5.09; N, 4.71. Found: 68.96; H, 4.82; N, 4.50. Compound 4f: IR (KBr): nmax = 3421, 3011, 2921, 1665, 1626, 1603, 1587, 1451 cm1. 1H NMR (400 MHz, CDCl3): d = d 3.01 (dd, 1 H, J = 17.1, 8.5 Hz, a-Ha), 3.09 (dd, 1 H, J = 17.1, 3.7 Hz, a-Hb), 3.78 (s, 3 H, OMe), 3.49 (d, 1 H, J = 2.8 Hz, OH), 5.19 (ddd, 1 H, J = 8.5, 3.7, 2.8 Hz, b-H),6.76 (d, 1 H, J = 16.1 Hz, a-H), 7.31-7.01 (m, 4 Harom, 3- MeOC6H4), 7.517.39 (m, 5 Harom, Ph), 7.59 (d, 1 H, J = 16.1 Hz, b-H). 13C NMR (100 MHz, CDCl3TMS): d = 49.5, 56.3, 70.3, 111.9, 114.7, 119.5, 126.7, 127.5, 128.1, 129.4, 130.3, 136.9, 141.5, 144.3, 161.3, 200.4. MS (EI): m/z = 282 [M+]. Anal. Calcd for C18H18O3: C, 76.57; H, 6.43. Found: C, 76.92; H, 6.33. Compound 4i: IR (KBr): nmax = 3441, 3027, 2920, 1679, 1618, 1606, 1584, 1458, 1349 cm1. 1H NMR (400 MHz, CDCl3): d = 3.09 (dd, 1 H, J = 17.5, 8.5 Hz, a-Ha), 3.19 (dd, 1 H, J = 17.5, 3.8 Hz, a-Hb), 3.49 (d, 1 H, J = 2.9 Hz, OH), 3.83 (s, 3 H, OMe), 5.21 (ddd, 1 H, J = 8.5, 3.8, 2.9 Hz, b- H), 6.69 (d, 1 H, J = 16.5 Hz, a-H), 6.93 (d, 2 Harom, J = 8.7 Hz, 4-MeOC6H4), 7.23 (d, 2 Harom, J = 8.7 Hz, 4-MeOC6H4), 7.62 (d, 2 Harom, J = 8.9 Hz, 4-O2NC6H4), 7.71 (d, 1 H, J = 16.5 Hz, b-H), 8.21 (d, 2 Harom, J = 8.9 Hz, 4-O2NC6H4).13C NMR (100 MHz, CDCl3TMS): d = 49.3, 60.1, 69.7, 115.2, 122.3, 126.9, 128.1, 129.3, 133.9, 142.3, 144.1, 148.4,159.8, 200.1. MS (EI): m/z = 327 [M+]. Anal. Calcd for C18H17NO5: C, 66.05; H, 5.23; N, 4.28. Found: C, 65.69; H, 5.34; N, 4.51. Compound 4o: IR (KBr): nmax = 3431, 3028, 2930, 1681, 1623, 1608, 1585, 1456, 1351 cm1. 1H NMR (400 MHz, CDCl3): d = 3.11 (dd, 1 H, J = 17.3, 9.2 Hz, a-Ha), 3.17 (dd, 1 H, J = 17.3, 3.1 Hz, a-Hb), 3.74 (d, 1 H, J = 3.0 Hz, OH), 5.43 (ddd, 1 H, J = 9.2, 3.1, 3.0 Hz, b-H), 6.78 (d, 1 H, J = 16.5 Hz, a-H), 7.63 (d, 1 H, J = 16.5 Hz, b-H), 8.297.71 (m, 8 Harom, 2 4-O2NC6H4). 13C NMR (100 MHz, CDCl3 TMS): d = 49.3, 69.5, 121.5, 122.3, 125.9, 127.9, 128.7, 142.4, 144.5, 146.2, 147.1, 147.9, 200.1. MS (EI): m/z = 342 [M+]. Anal. Calcd for C17H14N2O6: C, 59.65; H, 4.12; N, 8.18. Found: C, 59.90; H, 4.24; N, 7.91.