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24th July 2012 @ 12:49
START: Scheduled for 25/07/12 FINISH: [b][u]Hazard and Risk Assessment[/b][/u] [data]4704[/data] [b][u]Previous Experiments[/b][/u] [blog]6069[/blog] [blog]6137[/blog] [b][u]Chemical Information[/u][/b] [b]2-(3,4-dimethoxyphenyl)-N-(4-nitrobenzylidene)ethanamine (MNR42-1)[/b] - SMILES: O=[N+]([O-])C1=CC=C(/C=N/CCC2=CC(OC)=C(OC)C=C2)C=C1, InChI: InChI=1S/C17H18N2O4/c1-22-16-8-5-13(11-17(16)23-2)9-10-18-12-14-3-6-15(7-4-14)19(20)21/h3-8,11-12H,9-10H2,1-2H3/b18-12-, InChIKey: LMBMXYXQVBPKHJ-PDGQHHTCSA-N. [b]1-(6,7-dimethoxy-1-(4-nitrophenyl)-3,4-dihydroisoquinolin-2(1H)-yl)ethanone (KAB26-17) -[/b] SMILES: O=[N+]([O-])C1=CC=C(C2N(C(C)=O)CCC3=CC(OC)=C(OC)C=C32)C=C1, InChI: InChI=1S/C19H20N2O5/c1-12(22)20-9-8-14-10-17(25-2)18(26-3)11-16(14)19(20)13-4-6-15(7-5-13)21(23)24/h4-7,10-11,19H,8-9H2,1-3H3, InChIKey: OIFIJKJQAGAGKY-UHFFFAOYSA-N. [b]2,6-bis((R)-4-isopropyl-4,5-dihydrooxazol-2-yl)pyridine (([i]R[/i])-PyBOX)[/b] - SMILES: CC([C@@H]1COC(C2=CC=CC(C3=N[C@H](C(C)C)CO3)=N2)=N1)C, InChI: InChI=1S/C17H23N3O2/c1-10(2)14-8-21-16(19-14)12-6-5-7-13(18-12)17-20-15(9-22-17)11(3)4/h5-7,10-11,14-15H,8-9H2,1-4H3/t14-,15-/m0/s1, InChIKey: CSGQGLBCAHGJDR-GJZGRUSLSA-N. [b][u]Procedure[/b][/u] [i]NOTE: All THF was dried over microwave activated 3 Å molecular sieves (2.0-2.5 mm) >72 h prior to use. All acetonitrile was dried over microwave 3 Å molecular sieves (2.0-2.5 mm) >24 h prior to use.[1] All glassware used was dried overnight at 115 °C.[/i] [b]Catalyst Solution Preparation[/b] 2,6-Bis[(4[i]R[/i])-(+)-isopropyl-2-oxazolin-2-yl]pyridine (39 mg, 0.129 mmol, 2 equiv.) and Yb(OTf)3 (0.040 mg, 0.064 mmol, 1 equiv.) were dissolved in dried THF (1.9 mL) to give a chiral catalyst solution of 34 mM. To a mixture of 3 Å molecular sieves (~1.5 g) in MeCN (16 mL) was dissolved MNR42-1 (100 mg, 0.318 mmol, 1 equiv.). The mixture was cooled in an acetone ice bath (-10 °C) before the addition of acetyl chloride (0.04 mL, 0.6 mmol, 1.8 equiv.) and 2,6-lutidine (0.06 mL, 0.5 mmol, 1.6 equiv.). The catalyst solution (0.47 mL, 0.016 mmol, 0.05 equiv.) was added. The reaction mixture was allowed to warm to 25 °C and stirred under argon from 09:30. After 2 hours, the reaction mixture was diluted with EtOAc (15 mL). The mixture was washed with saturated sodium bicarbonate solution (15 mL). The organic layer was separated. The aqueous layer was extracted with EtOAc (3 × 15 mL). The organic layers were combined, dried (MgSO4) and concentrated under reduced pressure to yield crude KAB26-17 (176 mg, 155%). [b][u]Summary and Conclusion[/b][/u] [b][u]References[/b][/u] [1] D. Bradley, G. Williams and M. Lawton, [i]J. Org. Chem.[/i] [b]2010[/b], [i]75[/i], 8351. DOI: 10.1021/jo101589h [url=http://dx.doi.org/10.1021/jo101589h]Paper[/url]. [2] H. C. Aspinall, J. F. Bickley, N. Greeves, R. V. Kelly and P. M. Smith, [i]Organometallics[/i] [b]2005[/b], [i]24[/i], 3458. DOI: 10.1021/om050197+ [url=http://dx.doi.org/10.1021/om050197+]Paper[/url]. [3] H. Suga, K. Inoue, S. Inoue, A. Kakehi and M. Shiro, [i]J. Org. Chem.[/i] [b]2005[/b], [i]70[/i], 47. DOI: 10.1021/jo049007f [url=http://dx.doi.org/10.1021/jo049007f]Paper[/url] [4] Rare-Earth Metal Triflates in Organic Synthesis, S. Kobayashi, M. Sugiura, H. Kitagawa and W. W.-L. Lam, [i]Chem. Rev.[/i] [b]2002[/b], [i]102[/i], 2227–2302. DOI: 10.1021/cr010289i [url=http://dx.doi.org/10.1021/cr010289i]Paper[/url]. ------------------------------------------ NOTES ------------------------------------------
Attached Files
HRA KAB26-17
Scheme KAB26-17
Table KAB26-17
Scheme KAB26-17 (corrected)