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DOI: 10.1055/s-0031-1289857
Iron-Catalyzed Reductive Dehydroxylation of Benzylic Alcohols Using Polymethylhydrosiloxane (PMHS)
Publication History
Publication Date:
09 November 2011 (online)
Abstract
The combination of FeCl3 and PMHS is an efficient reducing system for the selective dehydroxylation of secondary benzylic alcohols, even in the presence of carbonyls, under very mild conditions.
Key words
reductive dehydroxylation - benzylic alcohol - siloxanes - FeCl3
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References and Notes
General procedure for the reductive dehydroxylation of benzylic alcohols 4: Anhydrous FeCl3 (2.4 mg, 0.015 mmol, 5 mol% equiv) was carefully weighed and stirred in 1,2-dichloroethane (2 mL) for 5 min. PMHS (0.05 mL, 0.9 mmol, 3.0 equiv) was then added to the prepared catalyst solution, followed by benzylic alcohol 4 (0.3 mmol, 1.0 equiv) and stirred at either r.t. or heated to the respective temperature. The residual crude product was concentrated in vacuo and purified by flash chromatography to afford the desired product 5. ¹H NMR and ¹³C NMR data of previously unknown compounds: 4-heptyl-1,2-dimethoxybenzene (5d). ¹H NMR (400 MHz, CDCl3): δ = 7.26-6.70 (m, 3 H), 3.87 (s, 3 H), 3.85 (s, 3 H), 2.54 (t, J = 7.8 Hz, 2 H), 1.60-0.86 (m, 13 H); ¹³C NMR (100 MHz, CDCl3): δ = 148.7, 147.0, 135.6, 120.1, 111.8, 111.2, 55.9, 55.8 35.6, 31.8, 31.7, 29.3, 29.2, 22.7, 14.1; HRMS (ESI): m/z [M + 1] calcd for C15H25O2: 237.1855; found: 237.1850. 1-Bromo-4-heptyl-benzene (5k):¹¹ ¹H NMR (400 MHz, CDCl3): δ = 7.37 (d, J = 8.3 Hz, 2 H), 7.03 (d, J = 8.3 Hz, 2 H), 2.54 (t, J = 7.8 Hz, 2 H), 1.63-1.53 (m, 2 H), 1.36-1.19 (m, 8 H), 0.88 (t, J = 6.8 Hz, 3 H); ¹³C NMR (100 MHz, CDCl3): δ = 141.8, 131.2, 130.1, 119.2, 35.3, 31.8, 31.3, 29.1, 29.1, 22.6, 14.1; HRMS (ESI): m/z [M + 1] calcd for C13H20Br: 255.0748; found: 255.0757.