RSS-Feed abonnieren
DOI: 10.1055/s-2001-15055
1,3-Dimethyl-2-phenylbenzimidazoline (DMPBI)-Acetic Acid: An Effective Reagent System for Photoinduced Reductive Transformation of α,β-Epoxy Ketones to β-Hydroxy Ketones
Publikationsverlauf
Publikationsdatum:
24. September 2004 (online)
![](https://www.thieme-connect.de/media/synthesis/200108/lookinside/thumbnails/10.1055-s-2001-15055-1.jpg)
Abstract
A combination of 1,3-dimethyl-2-phenylbenzimidazoline (DMPBI) and acetic acid has been utilized for photoinduced reductive transformation of α,β-epoxy ketones to β-hydroxy ketones. Study on photoreactions using several proton donors revealed that acetic acid is superior to other proton donors such as HCl, p-TsOH, MeOH, and water. 1,3-Dimethyl-2-phenylbenzimidazolium was produced in the reaction with acetic acid while N-benzoyl-N,N′-dimethyl-o-phenylenediamine was formed in aqueous solvents. When THF solutions containing aryl carbonyl possessing α,β-epoxy ketones and DMPBI and acetic acid were irradiated (λ > 280 nm), β-hydroxy ketones were isolated in good to excellent yields. Photosensitized conditions (λ > 340 nm) were employed for the reactions of alkyl carbonyl possessing α,β-epoxy ketones.
Key words
photoinduced electron transfer - 1,3-dimethyl-2-phenylbenzimidazoline - acetic acid - α,β-epoxy ketones - reductive ring opening - β-hydroxy ketones
-
1a
Padwa A. Organic Photochemistry Vol 1:Chapman OL. Marcel Dekker; New York: 1967. p.91 -
1b
Griffin GW. Organic Photochemistry Vol 3:Chapman OL. Marcel Dekker; New York: 1973. p.115 -
1c
Nastashi M.Streith J. Rearrangements in Ground and Excited States Vol. 3:deMayo P. Academic Press; New York: 1980. p.445 -
2a
Bodforss S. Chem. Ber. 1918, 51: 214 -
2b
Johnson CK.Domony B.Reush W. J. Am. Chem. Soc. 1963, 85: 3984 -
2c
Dunston JM.Yates P. Tetrahedron Lett. 1964, 505 -
2d
Padwa A. Tetrahedron Lett. 1964, 813 -
2e
Simikin RD.Zimmerman HE. Tetrahedron Lett. 1964, 1847 -
2f
Zimmerman HE.Cowley BR.Tseng CY.Wilson JW. J. Am. Chem. Soc. 1964, 86: 947 -
2g
Markos CS.Reush W. J. Am. Chem. Soc. 1967, 89: 3363 -
2h
Pappas SP.Gresham RM.Miller MJ. J. Am. Chem. Soc. 1970, 92: 5797 -
2i
Padwa A.Eisenhardt W. J. Am. Chem. Soc. 1971, 93: 1400 -
2j
Pete JP.Viriot-Villaum ML. Bull. Soc. Chim. Fr. 1971, 3699 -
2k
Pappas SP.Bao LO. J. Am. Chem. Soc. 1973, 95: 7906 -
2l
Venkataramani PS.Saxena NK.Srinivasan R.Ors J. J. Org. Chem. 1976, 41: 2784 -
2m
Dewar DJ.Sutherland RG. J. Chem. Soc., Perkin Trans. 2 1977, 1522 -
2n
Muzart J.Pete JP. Tetrahedron Lett. 1977, 303: 307 -
2o
Lee GA. J. Org. Chem. 1978, 43: 4256 -
2p
Hallet P.Muzart J.Pete JP. J. Org. Chem. 1981, 46: 4275 -
2q
Paquette LA.Nitz TJ.Ross RJ.Springer JP. J. Am. Chem. Soc. 1984, 106: 1446 -
2r
Kumar CV.Das PK.O’Sullivan WI.Ege SN.Griffin GW. J. Chem. Soc., Perkin Trans. 2 1984, 1745 -
2s
Kumar CV.Ramaiah D.Das PK.George MV. J. Org. Chem. 1985, 50: 2818 -
3a
Fieser LF. J. Am. Chem. Soc. 1953, 75: 4395 -
3b
Robinson CH.Henderson R. J. Org. Chem. 1972, 37: 565 -
3c
Weile GR.McMorris TC. J. Org. Chem. 1978, 43: 3942 -
3d
Shapiro EL.Gentles M.Kabasakalian P.Magatti A. J. Org. Chem. 1981, 46: 5017 -
3e
Osuka A.Takaoka K.Suzuki H. Chem. Lett. 1984, 271 -
3f
McChesney JD.Thompson TN. J. Org. Chem. 1985, 50: 3473 -
3g
Molander GA.Hahn G. J. Org. Chem. 1986, 51: 2596 -
3h
Miyashita M.Suzuki T.Yoshikoshi A. Tetrahedron Lett. 1987, 28: 4293 -
3i
Inokuchi T.Kusumoto M.Torii S. J. Org. Chem. 1990, 55: 1548 -
3k
Hasegawa E.Ishiyama K.Kato T.Horaguchi T.Shimizu T. J. Org. Chem. 1992, 57: 5352 -
3l
Engman L.Stern D. J. Org. Chem. 1994, 59: 5179 -
3m This transformation is still a topic in organic synthesis, the latest example (Cp2TiCl):
Hardouin C.Chevallier F.Rousseau B.Doris E. J. Org. Chem. 2001, 66: 1046 -
4a
Hasegawa E.Ishiyama K.Horaguchi T.Shimizu T. J. Org. Chem. 1991, 56: 1631 -
4b
Hasegawa E.Ishiyama K.Horaguchi T.Shimizu T. Tetrahedron Lett. 1991, 32: 2029 - 5
Cossy J.Bouzide A.Ibhi S.Aclinou P. Tetrahedron 1991, 47: 7775 - 6
Hasegawa E.Ishiyama K.Fujita T.Kato T.Abe T. J. Org. Chem. 1997, 62: 2396 -
7a
Chikashita H.Itoh K. Bull. Chem. Soc. Jpn. 1986, 59: 1747 -
7b
Chikashita H.Ide H.Itoh H. J. Org. Chem. 1986, 51: 5400 -
7c
Chen J.Tanner DD. J. Org. Chem. 1988, 53: 3898 -
7d
Chen J.Tanner DD. J. Org. Chem. 1989, 54: 3842 -
7e
Tanner DD.Chen J.Chen L.Luelo C. J. Am. Chem. Soc. 1991, 113: 8074 -
7f
Tanner DD.Chen J. J. Org. Chem. 1992, 57: 662 -
7g
Tanner DD.Chen J.Luelo C.Peters PM. J. Am. Chem. Soc. 1992, 114: 713 -
8a
Hasegawa E.Kato T.Kitazume T.Yanagi K.Hasegawa K.Horaguchi T. Tetrahedron Lett. 1996, 37: 7079 -
8b
Hasegawa E.Yoneoka A.Suzuki K.Kato T.Kitazume T.Yanagi K. Tetrahedron 1999, 55: 12957 - 9
Okada K.Okamoto K.Oda M. J. Am. Chem. Soc. 1988, 110: 8736 - 10
Mann CK.Barnes KK. Electrochemical Reactions in Nonaqueous Systems Marcel Dekker; New York: 1973. p.283 - 12
Zweig A.Maure AH.Roberts BG. J. Org. Chem. 1967, 32: 1322 -
13a
Craig JC.Ekwuribe N.Fu CC.Walker KAM. Synthesis 1981, 303 -
13b
Lee I.-SH.Jeoung EH.Kreevoy MM. J. Am. Chem. Soc. 1997, 119: 2722
References
Spectral and elemental analysis data of 1b, 1d, 1k, 1l and 2b, 2d, 2k, 2l were reported as Supplementary Material of reference 3k.