Subscribe to RSS
DOI: 10.1055/s-0029-1217048
Tandem Reactions of 2-Methylimidazoline and 1,2-Dimethylimidazoline with Various Benzoyl Chlorides
Publication History
Publication Date:
19 October 2009 (online)
![](https://www.thieme-connect.de/media/synthesis/201001/lookinside/thumbnails/10.1055-s-0029-1217048-1.jpg)
Abstract
The reactions of 2-methylimidazoline with excess benzoyl chlorides under mild conditions generated N,N′-diacyl-β-keto cyclic ketene-N,N′-acetals. Conversely, the corresponding reactions of 1,2-dimethylimidazoline under the same conditions stereoselectively formed the ring-opened (Z)-vinyl benzoates. The latter reactions feature the formation of carbon-carbon bonds, carbon-nitrogen bonds, and carbon-oxygen bonds in one sequential cascade.
Key words
acyl ketene-N,N′-acetal - carbon-carbon bond formation - 2-methylimidazoline - 1,2-dimethylimidazoline
- 1
McElvain SM.Tate BE. J. Am. Chem. Soc. 1945, 67: 202 - 2
Gruseck U.Heuschmann M. Chem. Ber. 1987, 120: 2053 - 3
Clemens DH.Bell AJ.O’Brien JL. J. Org. Chem. 1964, 29: 2932 - 4
Baganz H.Domaschke L. Chem. Ber. 1962, 95: 2095 - 5
Bredereck H.Effenberger F.Beyerlin HP. Chem. Ber. 1964, 97: 3081 - 6
Weingarten H.White WA. J. Org. Chem. 1966, 31: 2874 - 7
Hasek RH.Gott PG.Martin JC. J. Org. Chem. 1964, 29: 2513 - 8
Hall JH.Wojciechowska M. J. Org. Chem. 1978, 43: 4869 - 9
Armati A.De Ruggieri P.Rossi E.Stradi R. Synthesis 1986, 573 - 10
Rossi E.Pini E. Tetrahedron 1996, 52: 7939 - 11
Neidlein R.Klotz UJ. Chem. Ber. 1985, 118: 3217 - 12
Schoeni JP.Fleury JP. Tetrahedron 1975, 31: 671 - 13
Nakayama J.Akimoto K.Sugihara Y. Tetrahedron Lett. 1998, 39: 5587 - 14
Marcelis ATM.Van der Plas HC. Tetrahedron 1989, 45: 2693 - 15
Gruseck U.Heuschmann M. Chem. Ber. 1987, 120: 2065 - 16
Heuschmann M. Chem. Ber. 1988, 121: 39 - 17
Sauer J.Heldmann DK.Hetzenegger J.Krauthan J.Sichert H.Schuster J. Eur. J. Org. Chem. 1998, 12: 2885 - 18
Mueller K.Sauer J. Tetrahedron Lett. 1984, 25: 2541 - 19
Fioravanti S.Loreto MA.Pellacani L.Tardella PA. Heterocycles 1987, 25: 433 - 20
Rajagopalan P.Talaty CN. Tetrahedron Lett. 1966, 38: 4537 - 21
Gotthardt H.Flosbach C. Chem. Ber. 1988, 121: 951 - 22
Gotthardt H.Blum J. Chem. Ber. 1987, 120: 109 -
23a
Aspinall SR. J. Org. Chem. 1941, 6: 895 -
23b
Bergman J.Goonewardena H.Sjoeberg B. Heterocycles 1982, 19: 297 - 24
Zhou A.Pittman CU. Tetrahedron Lett. 2004, 45: 8899 - 25
Zhou A.Pittman CU. Synthesis 2006, 37 - 26
Zhou A.Pittman CU. Tetrahedron Lett. 2005, 46: 2045 - 27
Ye G.Zhou A.Henry WP.Song Y.Chatterjee S.Beard DJ.Pittman CU. J. Org. Chem. 2008, 73: 5170 -
28a
Tieman CH,Kollmeyer WD, andRoman SA. inventors; US 4002765. ; Chem. Abstr. 1977, 86, 134904 -
28b
Nutt DJ.French N.Handley S.Hudson A.Husband S.Jackson H.Jordan S.Lalies MD.Lewis J.Lione L.Mallard N.Prat J. Ann. N. Y. Acad. Sci. 1995, 763: 125 -
28c
Jonas J.-C.Garcia-Barrado M.-J.Angel I.Henquin J.-Cl. Eur. J. Pharmacol. 1994, 264: 81 -
28d
Venn RM.Bradshaw CJ.Spencer R.Brealey D.Caudwell E.Naughton C.Vedio A.Singer M.Feneck R.Treacher D.Willatts SM.Grounds RM. Anaesthesia 1999, 54: 1136 -
28e
Buerkle H.Yaksh T. Br. J. Anaesth. 1998, 81: 208 -
28f
Lemke KA. Can. Vet. J. 2004, 45: 475 -
28g
Emanuel B.Kompatscher P.Meyer VE. Plast. Reconstr. Surg. 2001, 108: 637 -
28h
Pigini M.Bousquet P.Brasili L.Carrieri A.Cavagna R.Dontenwill M.Gentili F.Giannella M.Leonetti F.Piergentili A.Quaglia W.Carotti A. Bioorg. Med. Chem. 1998, 6: 2245 -
28i
Van Zwieten PA. J. Hypertens. 1997, 15: 117 -
28j
LeBrigand L.Virsolvy A.Peyrollier K.Manechez D.Godfroid JJ.Guardiola Lemaitre B.Bataille D. Br. J. Pharmacol. 1997, 122: 786 -
28k
Molderings GJ.Donecker K.Burian M.Simon WA.Schroeder DW.Göthert M. J. Pharmacol. Exp. Ther. 1998, 285: 170 - Cyclic amidinium salts readily undergo ring-opening hydrolysis in the presence of water, see:
-
32a
DeWolfe RH.Cheng MWL. J. Org. Chem. 1969, 34: 2595 -
32b
DeWolfe RH. J. Am. Chem. Soc. 1960, 82: 1585 -
32c
Perrin CL.Thoburn JD. J. Am. Chem. Soc. 1993, 115: 3140 - 33
Forsberg JH.Spaziano VT.Balasubramanian TM.Liu GK.Kinsley SA.Duckworth CA.Poteruca JJ.Brown PS.Miller JL. J. Org. Chem. 1987, 52: 1017
References
X-ray crystallographic description of 12a: Crystal dimensions (mm): 0.38 × 0.35 × 0.22. C26H25.5N2O4.25; Mr = 433.98. Triclinic; space group P1; a = 8.571(2) Å, b = 10.140(2) Å, c = 14.383(3) Å; α = 103.687(3)˚, β = 106.909(3)˚, γ = 96.759(4)˚; V = 1138.5(4) ų; Z = 2; D(calcd) = 1.266 g/cm³; µ (mm-¹) = 0.086; F(000) = 459; Reflections collected/unique = 8421/4000; refinement method: full-matrix least-squares on F ²; final R indices [I > 2s (I)]. R1 = 0.0468, wR2 = 0.1099, R indices (all data) R1 = 0.1093, wR2 = 0.1370; goodness of fit on F² = 1.000. Crystals were grown by slow evaporization of pentane into a CHCl3-EtOAc solution of 12a. CCDC number for compound 12a is CCDC 683239. This data can be obtained free of charge from the Cambridge Crystallographic Data Centre via ww.ccdc.cam.ac.uk/datarequest/cif.
30SMART Version 5.625, SAINT+Version 6.22, 2001. Bruker Analytical X-ray Systems, Inc., Madison, Wisconsin, USA.
31G. M. Sheldrick; SHELXTL Version 6.1, 2000; Bruker Analytical X-ray Systems, Inc., Madison, Wisconsin, USA.