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DOI: 10.1055/s-2008-1072738
Polymer-Supported Synthesis of α- and β-Hydroxyketones through the Formation of 1,3-Dithiane Intermediates
Publication History
Publication Date:
16 April 2008 (online)
Abstract
The synthesis of polymer-supported 2-monosubstituted 1,3-dithianes from soluble copolymers bearing 1,3-propanedithiol groups, their lithiation, reactions with electrophiles such as aldehydes, ketones, α,β-unsaturated ketones and oxiranes, and cleavage of the produced dithioketal-protected α- or β-hydroxyketones with various reagents have been studied.
Key words
solid-phase synthesis - polymeric dithiols - polymeric dithianes - lithiation - umpolung
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References and Notes
Acetylation of Copolymer P3ad 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.
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3-Benzoyl-2-cyclohexen-1-ol (8ah)
Oil. IR (film, KBr): 3437 (OH), 1678 (CO) cm-1. 1H NMR (300 MHz, CDCl3): δ = 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): δ = 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.