Abstract
A novel, short synthetic route has been successfully developed
for a key precursor of Quinazolinap ligands. The key step is a Friedel-Crafts-type
reaction between 2-naphthol and 4-chloroquinazoline, with moderate
to quantitative yields recorded. A variation of this reaction allows
for the introduction of an amine group on the naphthalene unit.
Key words
arylation - Lewis acids - ligands - quinazolines - phenols
References and Notes
1a Jacobsen EN.
Pfaltz A.
Yamamoto H.
Comprehensive
Asymmetric Catalysis
Vol. 1:
Springer;
Berlin:
1999.
1b Jacobsen EN.
Pfaltz A.
Yamamoto H.
Comprehensive Asymmetric
Catalysis
Vol. 2:
Springer;
Berlin:
1999.
1c Jacobsen EN.
Pfaltz A.
Yamamoto H.
Comprehensive Asymmetric
Catalysis
Vol. 3:
Springer;
Berlin:
1999.
2a McCarthy M.
Guiry PJ.
Tetrahedron
2001,
57:
3809
2b Guiry PJ.
McCarthy M.
Lacey PM.
Saunders CP.
Kelly S.
Connolly DJ.
Curr.
Org. Chem.
2000,
4:
835
2c Saunders CP.
Guiry PJ.
Adv.
Synth. Catal.
2004,
346:
497
2d Li Y.-M.
Kwong F.-Y.
Yu W.-Y.
Chan ASC.
Coord. Chem.
Rev.
2007,
251:
2119
3a Alock NW.
Brown JM.
Hulmes DI.
Tetrahedron: Asymmetry
1993,
4:
743
3b Brown JM.
Hulmes DI.
Guiry PJ.
Tetrahedron
1994,
50:
4493
4 Doucet H.
Fernandez E.
Layzell TP.
Brown JM.
Chem. Eur. J.
1999,
5:
1320
5 Gommermann N.
Koradin C.
Polborn K.
Knochel P.
Angew. Chem. Int. Ed.
2003,
42:
5763
6 Morgan JB.
Miler SP.
Morken JP.
J. Am. Chem. Soc.
2003,
125:
8702
7 Chen C.
Li X.
Schreiber SL.
J.
Am. Chem. Soc.
2003,
125:
10174
8a McCarthy M.
Goddard R.
Guiry PJ.
Tetrahedron: Asymmetry
1999,
10:
2797
8b Lacey PM.
McDonnell C.
Guiry PJ.
Tetrahedron Lett.
2000,
41:
2457
8c Connolly DJ.
Lacey PM.
McCarthy M.
Saunders CP.
Carroll AM.
Goddard R.
Guiry PJ.
J. Org. Chem.
2004,
69:
6572
8d Flanagan SP.
Goddard R.
Guiry PJ.
Tetrahedron
2005,
61:
9808
8e Fekner T.
Müller-Bunz H.
Guiry PJ.
Org. Lett.
2006,
8:
5109
8f Maxwell AC.
Franc C.
Pouchain L.
Müller-Bunz H.
Guiry PJ.
Org. Biomol. Chem.
2008,
6:
3848
8g Fekner T.
Müller-Bunz H.
Guiry PJ.
Eur. J. Org. Chem.
2008,
5055
8h McCarthy M.
Hooper MW.
Guiry PJ.
Chem. Commun.
2000,
1333
8i Maxwell AC.
Flanagan SP.
Goddard R.
Guiry PJ.
Tetrahedron:
Asymmetry
2010,
21:
1458
8j Fleming WJ.
Muller-Bunz H.
Guiry PJ.
Eur. J. Org. Chem.
2010,
5996
9 Pal M.
Batchu VR.
Parasuraman K.
Yeleswarapu KR.
J. Org. Chem.
2003,
68:
6806
10a Knopfel TF.
Aschwanden P.
Ichikawa T.
Watanabe T.
Carreira EM.
Angew. Chem. Int.
Ed.
2004,
43:
5971
10b Knopfel TF.
Zarotti P.
Ichikawa T.
Carreira EM.
J.
Am. Chem. Soc.
2005,
127:
9682
10c Carreira EM. inventors;
US Patent, 20050277772 .
,
11 Hentrich W, Hardtmann M, and Knoche R. inventors; US
Patent, 1780879.
12 Kumar S.
Sahu DP.
J. Heterocycl. Chem.
2009,
46:
748
13a Mintas M.
Mihaljevic V.
J.
Chem. Soc., Perkin Trans. 2
1990,
619
13b Harmange J.-C.
Weiss MM.
Germain J.
Polverino AJ.
Borg G.
Bready J.
Chen D.
Choquette D.
Coxon A.
DeMelfi T.
DiPietro L.
Doerr N.
Estrada J.
Flynn J.
Graceffa RF.
Harriman SP.
Kaufman S.
La DS.
Long A.
Martin MW.
Neervannan S.
Patel VF.
Potashman M.
Regal K.
Roveto PM.
Schrag ML.
Starnes C.
Tasker A.
Teffera Y.
Wang L.
White RD.
Whittington DA.
Zanon R.
J. Med. Chem.
2008,
51:
1649
13c Hennequin
LFA. inventors; US Patent 20080058342.
14 Beugelmans R.
Bois-Choussy M.
J. Org. Chem.
1991,
56:
2518
15
Typical Procedure :
2-Naphthol (1 mmol), 4-chloroquinaz-oline (1 mmol) and AlCl3 (3
mmol) were suspended in DCE (3 mL) in a Schlenk tube under a nitrogen
atmosphere. The mixture was heated at 80 ˚C for 3.5 h and
then diluted with CH2 Cl2 (15 mL). The mixture
was washed with 1 M NaOH solution (15 mL), sat. NH4 Cl
solution (15 mL), H2 O (15 mL), brine (15 mL), dried over
MgSO4 , filtered and eva-porated under reduced pressure.
The crude product could be directly used in the subsequent steps
of the synthesis without significant loss of yield compared to the
use of pure compound. Nevertheless, purification was achievable
by column chromatography using silica gel and CH2 Cl2 as eluent.
Compounds were identical to known samples.
