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24th July 2012 @ 12:49
START: Scheduled for 25/07/12


Hazard and Risk Assessment
HRA KAB26-17

Previous Experiments
Preparation of MNR42-1
Yb(OTf)3 (THF solution) catalysed acyl-PS formation of KAB26-16 in MeCN

Chemical Information
2-(3,4-dimethoxyphenyl)-N-(4-nitrobenzylidene)ethanamine (MNR42-1) - 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.
1-(6,7-dimethoxy-1-(4-nitrophenyl)-3,4-dihydroisoquinolin-2(1H)-yl)ethanone (KAB26-17) - 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.
2,6-bis((R)-4-isopropyl-4,5-dihydrooxazol-2-yl)pyridine ((R)-PyBOX) - 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.

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.

2,6-Bis[(4R)-(+)-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.

Catalyst Solution Preparation

Summary and Conclusion

[1] D. Bradley, G. Williams and M. Lawton, J. Org. Chem. 2010, 75, 8351. DOI: 10.1021/jo101589h Paper.
[2] H. C. Aspinall, J. F. Bickley, N. Greeves, R. V. Kelly and P. M. Smith, Organometallics 2005, 24, 3458. DOI: 10.1021/om050197+ Paper.
[3] H. Suga, K. Inoue, S. Inoue, A. Kakehi and M. Shiro, J. Org. Chem. 2005, 70, 47. DOI: 10.1021/jo049007f Paper
[4] Rare-Earth Metal Triflates in Organic Synthesis, S. Kobayashi, M. Sugiura, H. Kitagawa and W. W.-L. Lam, Chem. Rev. 2002, 102, 2227–2302. DOI: 10.1021/cr010289i Paper.

Linked Posts
Attached Files
HRA KAB26-17
Scheme KAB26-17
Table KAB26-17
Scheme KAB26-17 (corrected)