1144
V. Bertini et al.
LETTER
cess, probably through a Grob fragmentation17,18 made
possible by the nature of the substituents.
(7) Corey, E. J.; Erickson, B. W. J. Org. Chem. 1971, 36, 3553.
(8) Bulman Page, P. C.; Graham, A. E.; Park, K. B. Tetrahedron
1992, 48, 7265.
(9) Stork, G.; Zhao, K. Tetrahedron Lett. 1989, 30, 287.
(10) Acetylation of Copolymer P3ad
In conclusion, polymer-supported dithioketal-protected
a- or b-hydroxyketones (P3–P7) were very satisfactorily
prepared starting from the 1,3-propanedithiol copolymer
P1. The recovery of the hydroxyketones from the copoly-
mers was characteristic of 1,3-dithiane small molecule
chemistry.6 The hydroxy group of the dithioketal-protect-
ed hydroxyketones, as exemplified with the preparation of
P7ad, could be exploited for further transformations po-
tentially useful in the field of combinatorial chemistry.
A mixture of P3ad (0.483 g), anhyd pyridine (7.5 mL), and
Ac2O (0.7 mL) was left 3 d at r.t., precipitated in H2O (80
mL), washed with H2O, then with MeOH, and pump-dried
up to constant weight to afford P6ad (0.495 g). IR (KBr):
1747, 1226 (ester) cm–1.
(11) Ostrowski, P. C.; Kane, V. V. Tetrahedron Lett. 1977, 3549.
(12) Sikorski, W. H.; Reich, H. J. J. Am. Chem. Soc. 2001, 123,
6527.
(13) 3-Benzoyl-2-cyclohexen-1-ol (8ah)
Oil. IR (film, KBr): 3437 (OH), 1678 (CO) cm–1. 1H NMR
(300 MHz, CDCl3): d = 1.55–1.76 (m, 2 H, 5-H and 6-H),
1.81–1.95 (m, 1 H, 5-H), 1.95–2.06 (m, 1 H, 6-H), 2.13 (br,
1 H, OH), 2.40 (m, 2 H, 4-H), 4.43 (br m, 1 H, 1-H), 6.43 (m,
1 H, 2-H), 7.37–7.55 (m, 3 H, arom. H), 7.65–7.70 (m, 2 H,
arom. H). 13C NMR (75.5 MHz, CDCl3): d = 19.1 (5-C),
24.2 (4-C), 31.4 (6-C), 66.3 (1-C), 128.2 (3¢-C), 129.3 (2¢-
C), 131.9 (4¢-C), 137.7 (3-C or 1¢-C), 139.9 (1¢-C or 3-C),
142.6 (2-C), 198.2 (C=O, ketone). MS (EI): m/z (%) = 202
(41) [M+]. Anal. Calcd for C13H14O2: C, 77.20; H, 6.98.
Found: C, 77.01; H, 7.02.
Acknowledgment
This work was financially supported by MIUR (Programmi di
Ricerca di Rilevante Interesse Nazionale 2006) and University
Funds.
References and Notes
(1) Bertini, V.; Lucchesini, F.; Pocci, M.; De Munno, A.
Tetrahedron Lett. 1998, 39, 9263.
(2) Bertini, V.; Lucchesini, F.; Pocci, M.; De Munno, A. J. Org.
Chem. 2000, 65, 4839.
(3) Bertini, V.; Pocci, M.; Lucchesini, F.; Alfei, S.; De Munno,
A. Synlett 2003, 1201.
(4) Eliel, E. L.; Hartmann, A. A.; Abatjoglou, A. G. J. Am.
Chem. Soc. 1974, 96, 1807.
(5) Lucchesini, F.; Bertini, V.; Pocci, M.; Micali, E.; De Munno,
A. Eur. J. Org. Chem. 2002, 1546.
(6) Bulman Page, P. C.; Van Niel, M. B.; Prodger, J. C.
Tetrahedron 1989, 45, 7643.
(14) Tenza, K.; Northen, J. S.; O’Hagan, D.; Slawin, A. M. Z.
J. Fluorine Chem. 2004, 125, 1779.
(15) Reeve, W.; Christoffel, I. J. Am. Chem. Soc. 1950, 72, 1480.
(16) Fukuzawa, S.; Sakai, S. Bull. Chem. Soc. Jpn. 1992, 65,
3308.
(17) De Dobbeleer, C.; Ates, A.; Vanherk, J.-C.; Markò, I. E.
Tetrahedron Lett. 2005, 46, 3889.
(18) Barluenga, J.; Álvarez-Pérez, M.; Wuerth, K.; Rodriguez,
F.; Fañanás, F. Org. Lett. 2003, 5, 905.
Synlett 2008, No. 8, 1141–1144 © Thieme Stuttgart · New York