Biaryl Coupling Reactions Catalyzed by Diazadecalins
SCHEME 1
SCHEME 2 a
a
Reagents and conditions: (a) (7f) BnBr, KOH, MeOH, reflux,
4 h, 50%. (7g) o-MeOPhCH2Br, KOH, MeOH, reflux, 1 d, 29%.
(7g f 7h ) BBr3, 1 d, 29%.
al.9c,d demonstrated that catalytic coupling of 3-car-
boalkoxy-2-naphthols with good enantioselectivity is pos-
sible using prolyldiamine (3) or sparteine (5) derived
copper oxidants (Scheme 1). In a further advance, we
have found that 1,5-diaza-cis-decalin 6 copper catalysts
are highly selective in this reaction (eq 1).13 By imple-
menting several modifications, a variety of novel 3,3′-
disubstituted BINOL derivatives can be synthesized. In
this paper, we disclose the full results of these studies.
Ch ir a l Dia m in es. Few significantly different chiral
diamines have found general utility in asymmetric
synthesis. The most widely used versions (1-5) are
shown in Scheme 1.14,15 We identified scaffold 6 as a
potential lead from our efforts in the computer-aided
identification of novel ligands.16 We have demonstrated
that diaza-cis-decalins 617 are moderately effective in
asymmetric lithiation-substitution18 and highly effective
in the enantioselective oxidative biaryl coupling of sub-
stituted 2-naphthol derivatives.13a Here, the development
of the diaza-cis-decalin copper catalysts for the enantio-
selective oxidative coupling of a variety of functionalized
2-naphthols is presented.
Resu lts a n d Discu ssion
Meta l a n d Liga n d Su r vey. Enantiomerically pure
(S,S)-1,5-diaza-cis-decalin 7a and its antipode (R,R)-7a
are readily synthesized from commercial materials in
three steps.18a The ligands 7b-e (Scheme 2) were pre-
pared from this material as described previously.13a,18a
Ligands 7f and 7g were prepared by N-alkylation as
shown in Scheme 2.
To survey the utility of the 1,5-diaza-cis-decalin struc-
ture, a number of oxidative metal complexes were
formulated using chiral 7a (Table 1, entries 1-3). The
manganese,19 iron,20 and copper complexes all provided
some selectivity in the oxidative biaryl coupling of
3-methoxycarbonyl-2-naphthol (8a ) with oxygen as the
terminal oxidant (eq 1). The copper catalyst gave the
(8) One of the most efficient routes to enantiomerically pure BINOL
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2126. For other resolution methods, see: (b) Periasamy, M.; Venkatra-
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Lett. 1995, 7991-7994. (f) Kawashima, M.; Hirayama, A. Chem. Lett.
1990, 2299-2300.
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S.-I.; Noji, M.; Koga, K. J . Org. Chem. 1999, 64, 2264-2271 (10 mol %
catalyst, 78% ee for 9a , 17% ee for BINOL). (e) Irie, R.; Masutani, K.;
Katsuki, I. Synlett 2000, 1453-1436 (2 mol % catalyst, 65% ee for
BINOL). (f) Chu, C.-Y.; Hwang, D.-R.; Wang, S.-K.; Uang, B.-J . Chem.
Commun. 2001, 980-981 (2 mol % catalyst, 51% ee for BINOL). (g)
Hon, S.-W.; Li, C.-H.; Kuo, J .-H.; Barhate, N. B.; Liu, Y.-H.; Wang, Y.;
Chen, C.-T. Org. Lett. 2001, 3, 869-872 (10 mol % catalyst, 62% ee
for BINOL). (h) Luo, Z.; Liu, Q.; Gong, L.; Cui, X.; Mi, A.; J iang, Y.
Chem. Commun. 2002, 914-915 (10 mol % catalyst, 6 d, 83% ee for
BINOL). (i) Barhate, N. B.; Chen, C.-T. Org. Lett. 2002, 4, 2529-2532
(10 mol % catalyst, 15 d, 87% ee for BINOL). (j) Luo, Z. B.; Liu, Q. Z.;
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Chu, C.-Y.; Uang, B.-J . Tetrahedron: Asymmetry 2003, 14, 53-55 (10
mol % catalyst, 73% ee for BINOL).
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terminal oxidant.
a copper catalyst using AgCl as the
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J . Org. Chem, Vol. 68, No. 14, 2003 5501