4384
A. N. Cammidge, K. V. L. Cr e´ py / Tetrahedron 60 (2004) 4377–4386
boronic acid 18 (0.8 g, 4.33 mmol), barium hydroxide octa-
hydrate (1.86 g, 5.91 mmol), palladium chloride (20.9 mg,
Using Ba(OH) ·8H O/toluene/EtOH/H O (Table 3, entry 3).
2 2 2
2-Methylnaphth-1-yl boronic acid 18 (0.18 g, 0.87 mmol),
barium hydroxide octahydrate (0.37 g, 1.19 mmol),
0
1
.12 mmol), triphenylphosphine (61.9 mg, 0.24 mmol),
-iodonaphthalene 24 (1 g, 3.94 mmol), DME (25 mL)
0
0
[(R)-(þ)-2,2 -bis(diphenylphosphino)-1,1 -binaphthyl]pal-
ladium(II) chloride 1 (18.9 mg, 0.02 mmol), 1-iodonaph-
thalene 24 (0.2 g, 0.79 mmol), toluene (3 mL), ethanol
(3 mL) and water (1 mL) were heated under reflux overnight
and worked up according to the general procedure. The
crude oil was purified by column chromatography over
silica gel (eluting with distilled hexane) to give the title
and water (4 mL) were heated under reflux overnight and
worked up according to the general procedure. The crude oil
was purified by column chromatography over silica gel
(
(
8
eluting with petroleum ether) to give the title compound
9
2
645 mg, 61%) as a white solid, mp 82.8–87.1 8C (lit.,
6–88 8C; d (300 MHz; CDCl ) 2.11 (3H, s), 7.13–7.65
H
3
2
2
(
8H, m), 7.61 (1H, dd, J¼7.0, 1.3 Hz), 7.88 (2H, d, J¼
compound (100 mg, 47%) as a white solid, [a] ¼þ3.4 (c
D
8
1
1
1
.4 Hz) and 7.96 (2H, d, J¼8.4 Hz); d (67.9 MHz) 20.4,
0.37, CHCl ), optical purity 8%.
3
C
24.9, 125.7, 125.9, 126.0, 126.1, 126.2, 126.3, 127.6,
27.7, 127.8, 127.8, 128.3, 128.7, 132.1, 132.7, 133.556,
33.8, 134.5, 136.2 and 137.6.
(b) With (þ)-(S)-(R)-PFNMe 4.
0
0
30
4
.3.1.2. (6)-2,2 -Dimethyl-1,1 -binaphthalene 26 —
Using Ba(OH) ·8H O/DME/H O (Table 3, entry 4). 2-Methyl-
2
2
2
representative procedure (Table 2, entry 6). 2-Methyl-
naphth-1-yl(pinacol)boronate ester 20 (0.22 g, 0.82 mmol),
cesium fluoride (0.25 g, 1.64 mmol), palladium chloride
naphth-1-yl boronic acid 18 (0.24 g, 1.3 mmol), barium
hydroxide octahydrate (0.56 g, 1.77 mmol), palladium
chloride (6.3 mg, 0.03 mmol), (þ)-(S)-N,N-dimethyl-1-
[(R)-2-diphenylphosphino)ferrocenyl]ethylamine 4 (31.3 mg,
0.06 mmol), 1-iodonaphthalene 24 (0.3 g, 1.18 mmol),
DME (7 mL) and water (2 mL) were heated under reflux
overnight and worked up according to the general
procedure. The crude oil (0.38 g) was purified by column
chromatography over silica gel (eluting with distilled
hexane) to give the title compound (144 mg, 44%) as a
(
2.2 mg, 0.01 mmol), triphenylphosphine (6.5 mg, 0.02
mmol), 1-iodo-2-methylnaphthalene 17 (0.15 g, 0.41 mmol)
and DME (5 mL) were heated under reflux for 3 days and
worked up according to the general procedure. The brown
oil was purified by column chromatography over silica gel
(
(
eluting with petroleum ether) to give the title compound
86 mg, 36%) as a colourless oil; dH (300 MHz; CDCl3)
2
2
1
.96 (6H, s), 6.90 (2H, d, J¼8.3 Hz), 7.13 (2H, m), 7.32
white solid, [a] ¼227.7 (c 0.39, CHCl ), optical purity
D
3
(
2H, m), 7.44 (2H, d, J¼8.4 Hz) and 7.82 (4H, dd, J¼7.4,
63%.
4
.1 Hz).
Using CsF/DME (Table 3, entry 6). 2-Methylnaphth-1-yl
boronic acid 18 (0.44 g, 2.36 mmol), cesium fluoride
(0.72 g, 4.72 mmol), palladium chloride (6.3 mg,
0.04 mmol), (þ)-(S)-N,N-dimethyl-1-[(R)-2-diphenylphos-
phino)ferrocenyl]ethylamine 4 (31.3 mg, 0.07 mmol),
1-iodonaphthalene 24 (0.3 g, 1.18 mmol) and DME
(7 mL) were heated under reflux overnight and worked up
according to the general procedure. The crude oil was
purified by column chromatography over silica gel (eluting
with distilled hexane) to give the title compound (138 mg,
4.3.2. Asymmetric couplings. Optical purities were
determined by optical rotation; 2-methyl-1,1 -binaphthalene
0
0
7
a
22
0
29
2
5 lit., [a] ¼243.9 (c 1.0, CHCl ); 2,2 -dimethyl-1,1 -
D
3
7
a
22
D 3
binaphthalene 26 (lit., [a] ¼235.6 (c 1.0, CHCl ), lit.,
2
2
[
a] ¼219.0 (c 1.3, ethanol)).
D
0
4.3.2.1. 2-Methyl-1,1 -binaphthalene 25—representa-
tive procedures.
(
a) With (R)-(þ)-BINAP 1.
2
2
4
4%) as a white solid, [a] ¼224.2 (c 0.38, CHCl ), optical
D
3
Using Ba(OH) ·8H O/DME/H O (Table 3, entry 1). 2-Methyl-
2
purity 55%.
2
2
naphth-1-yl boronic acid 18 (0.4 g, 2.17 mmol), barium
hydroxide octahydrate (0.93 g, 2.96 mmol), [(R)-(þ)-2,2 -
0
bis(diphenylphosphino)-1,1 -binaphthyl]palladium(II)
Using Ba(OH) ·8H O/toluene/EtOH/H O (Table 3, entry 7).
2 2 2
0
chloride 1 (47.3 mg, 0.06 mmol), 1-iodonaphthalene 24
2-Methylnaphth-1-yl boronic acid 18 (0.18 g, 0.87 mmol),
barium hydroxide octahydrate (0.37 g, 1.18 mmol), palla-
dium chloride (4.2 mg, 0.02 mmol), (þ)-(S)-N,N-dimethyl-
(
0.5 g, 1.97 mmol), DME (12 mL) and water (3 mL) were
heated under reflux overnight and worked up according to
the general procedure. The crude oil (0.56 g) was purified
by column chromatography over silica gel (eluting with
distilled hexane) to give the title compound (290 mg, 55%)
1-[(R)-2-diphenylphosphino)ferrocenyl]ethylamine
4
(20.8 mg, 0.05 mmol), 1-iodonaphthalene 24 (0.2 g,
0.79 mmol) and toluene (3 mL), ethanol (3 mL) and water
(1 mL) were heated under reflux overnight and worked up
according to the general procedure. The crude oil was
purified by column chromatography over silica gel (eluting
with distilled hexane) to give the title compound (94 mg,
2
2
as a white solid, [a] ¼þ10.9 (c 0.36, CHCl ), optical
D
3
purity 25%.
2
2
Using CsF/DME (Table 3, entry 2). 2-Methylnaphth-1-yl
boronic acid 18 (0.18 g, 0.87 mmol), cesium fluoride
45%) as a white solid, [a] ¼222.8 (c 0.35, CHCl ), optical
D
3
purity 52%.
0
,1 -binaphthyl]palladium(II) chloride 1 (18.9 mg, 0.02
(
1
0.24 g, 1.57 mmol), [(R)-(þ)-2,2 -bis(diphenylphosphino)-
0
(c) With (þ)-(S)-(R)-PFOMe 5 (Table 3, entry 9).
mmol), 1-iodonaphthalene 24 (0.2 g, 0.79 mmol) and DME
5 mL) were heated under reflux overnight and worked up
(
2-Methylnaphth-1-yl boronic acid 18 (0.34 g, 1.82 mmol),
barium hydroxide octahydrate (0.86 g, 2.72 mmol),
palladium chloride (4.8 mg, 0.03 mmol), (þ)-(S)-1-[(R)-2-
(diphenylphosphino)ferrocenyl]ethyl methyl ether 5
(23.3 mg, 0.06 mmol), 1-iodonaphthalene 24 (0.23 g,
according to the general procedure. The crude oil was puri-
fied by column chromatography over silica gel (eluting with
distilled hexane) to give the title compound (90 mg, 43%) as
2
2
a white solid, [a] ¼þ9.1 (c 0.22, CHCl ), optical purity 21%.
D
3