Xing Dai and Huw M. L. Davies
FULL PAPERS
(S)-2,2’-dimethoxy-1,1’dinaphthyl (3.0 g, 9.5 mmol) was
added in one portion, and the reaction mixture was stirred
for 3 h. The resulting light brown suspension was cooled to
3-(But-3-enyl)bicyclo[3.2.1]oct-6-en-2-one (5h)
G
Aluminum chloride powder (49 mg, 1.1 equivs.) was added
in one portion to a stirred solution of 2-methylenehex-5-
enal (4h) (37 mg, 0.33 mmol) in dry CH2Cl2 (3 mL) in a 10-
mL round-bottom flask at À788C. Freshly distilled and pre-
cooled cyclopentadiene (56 mg, 0.84 mmol) was then added
dropwise by syringe to the reaction mixture. After 60 min at
À788C, the reaction was gradually warmed to 08C in
10 min. Then the mixture was kept at the same temperature
for 50 min. The reaction was then quenched with saturated
sodium bicarbonate solution (5 mL) and extracted with
ether (2), and the combined extracts were washed with
water and brine, dried over MgSO4, and concentrated. The
crude product was purified by column chromatography on
silica gel using pentane-diethyl ether (98:2 to 93:7) as eluent
to give 5h as a colorless oil; yield: 49 mg (83% yield).
1H NMR (500 MHz, CDCl3): d=6.25 (dd, J=5.5, 3.0 Hz,
1H), 5.81 (dd, J=5.5, 3.0 Hz, 1H), 5.76 (m, 1H), 5.00 (m,
1H), 4.95 (m, 1H), 3.07 (t, J=3.5 Hz, 1H), 2.79 (m, 1H),
2.51 (m, 1H), 2.24–2.16 (m, 2H), 2.13 (d, J=11.5 Hz, 1H),
2.09–2.03 (m, 1H), 1.99–1.89 (m, 2H), 1.45–1.37 (m, 1H),
1.31–1.23 (m, 1H); 13C NMR (75 MHz, CDCl3): d=208.5,
140.8, 138.2, 129.9, 114.9, 54.6, 44.6, 37.7, 37.2, 33.9, 30.8,
30.4; IR (neat). n=2943, 1705 (C=O) cmÀ1; HR-MS(EI):
m/z=176.1196, calcd. for C12H16O [M]+: 176.1196.
À788C, and B
A
over a period of 10 min. The solution was allowed to warm
to room temperature and was left stirring overnight. The re-
action mixture was cooled to 08C, 1m HCl (75 mL) was
added, and the reaction mixture was stirred for 2 h. The
phases were separated, and the organic phase was washed
twice with 1m HCl (50 mL) and saturated aqueous NaCl
(50 mL) and dried over Na2SO4. The solvent was removed
under reduced pressure, and the resulting white solid was re-
crystallized from toluene to give (S)-3,3’-bis(dihydroxybor-
ane)-2,2’-dimethoxy-1,1’-dinaphthyl as white crystals; yield:
2.84 g (76%). The physical and spectral data were identical
to those previously reported for this compound.[27] 1H NMR
(500 MHz, CDCl3): d=8.62 (s, 2H), 7.99 (d, J=8.0 Hz, 2H),
7.44 (t, J=7.5 Hz, 2H), 7.32 (td, J=7.5, 1.0 Hz, 2H), 7.16
(d, J=8.0 Hz, 2H), 6.00 (s, 4H, OH), 3.31 (s, 6H).
In a 50-mL, two-necked flask equipped with a condenser
were placed (S)-3,3’-bis(dihydroxyborane)-2,2’-dimethoxy-
1,1’-dinaphthyl (950 mg, 2.40 mmol), Ba(OH)2·8H2O (2.28 g,
7.22 mmol), and Pd(PPh3)4 (278 mg, 0.24 mmol), and the
N
flask was evacuated and filled with argon three times. 1,4-
Dioxane (15 mL), H2O (5 mL), and 1-bromo-2-methoxyben-
zene (1.80 g, 9.62 mmol) were added. The reaction mixture
was refluxed for 24 h under argon and cooled to room tem-
perature. The dioxane was removed, and the resulting phase
was redissolved in CH2Cl2 (75 mL), washed with 1M HCl
(250 mL) and saturated aqueous NaCl (75 mL), and dried
over Na2SO4. The solvent was removed to give the crude
product as a yellow semicrystalline oil. The crude product
was purified by column chromatography on silica gel using
1/12 to 1/8 EtOAc/hexanes as eluent to give (S)-3,3’-bis(2-
methoxy-phenyl)-2,2’-dimethoxy-1,1’-binaphthyl as pale
white solid; yield: 703 mg (56%). 1H NMR (500 MHz,
CDCl3): d=7.89 (s, 2H), 7.87 (d, J=8.0 Hz, 2H), 7.47 (dd,
J=7.5, 2.0 Hz, 2H), 7.40–7.35 (m, 4H), 7.33 (d, J=8.0 Hz,
2H), 7.26 (m, 2H), 7.05 (t, J=8.0 Hz, 2H), 7.00 (d, J=
8.0 Hz, 2H), 3.77 (s, 6H), 3.19 (s, 6H); 13C NMR (125 MHz,
CDCl3): d=157.2, 154.9, 133.8, 132.5, 131.3, 130.8, 130.5,
128.8, 128.4, 127.9, 125.9, 125.8, 124.8, 124.5, 120.4, 110.9,
3-[(Z)-Pent-2-enyl]bicyclo[3.2.1]oct-6-en-2-one (5i)
G
Aluminum chloride powder (71 mg, 1.1 equivs.) was added
in one portion to a stirred solution of (Z)-2-methylenehept-
4-enal (4i) (60 mg, 0.48 mmol) in dry CH2Cl2 (4 mL) in a 10-
mL round-bottom flask at À788C. Freshly distilled and pre-
cooled cyclopentadiene (160 mg, 2.42 mmol) was then added
dropwise by syringe to the reaction mixture. After 60 min at
À788C, the reaction was gradually warmed to 08C in
15 min. Then at the reaction was kept at the same tempera-
ture for 45 min. The reaction was then quenched with satu-
rated sodium bicarbonate solution (5 mL) and extracted
with ether (2), and the combined extracts were washed
with water and brine, dried over MgSO4, and concentrated.
The crude product was purified by column chromatography
on silica gel using pentane-diethyl ether (98:2 to 93:7) as
eluent to give 5i as a colorless oil; yield: 83 mg (91%);
1H NMR (500 MHz, CDCl3): d=6.26 (dd, J=5.5, 3.0 Hz,
1H), 5.81 (dd, J=5.5, 3.0 Hz, 1H), 5.43 (m, 1H), 5.17 (m,
1H), 3.08 (t, J=4.0 Hz, 1H), 2.77 (m, 1H), 2.57 (m, 1H),
2.47 (m, 1H), 2.24–2.09 (m, 3H), 2.15 (d, J=11.0 Hz, 1H),
2.00 (dt, J=7.5, 7.5 Hz, 2H), 1.30 (m, 1H), 0.94 (d, J=
7.5 Hz, 3H); 13C NMR (75 MHz, CDCl3): d=207.9, 140.8,
133.4, 129.7, 126.1, 54.5, 45.3, 37.6, 37.2, 31.8, 29.6, 20.6,
14.2; IR (neat): n=2960, 1707 (C=O), 1451 cmÀ1; HR-MS
(EI): m/z: 190.1355, calcd. for C13H18O [M]+: 190.1352.
60.5, 55.7; HR-MS(EI)S:
m/z: 549.2052, calcd. for
C36H30O4Na [M+Na]+: 549.2036.
To a solution of (S)-3,3’-bis(2-methoxy-phenyl)-2,2’-dime-
thoxy-1,1’-binaphthyl (703 mg, 1.33 mmol) in DCM (10 mL)
at À788C, was added BBr3 (10.7 mL. 1.0m in DCM) drop-
wise. The reaction was allowed to warm to 08C over 2 h.
After stirring at 08C for 30 min, the reaction was poured
into 50 mL ice/water. The mixture was extracted with ether
(2), and the combined extracts were washed with water
and brine, dried over Na2SO4, and concentrated. The result-
ing yellow solid was chromatographed on silica to give (S)-
3,3’-di(2-hydroxyphenyl)-2,2’- dihydroxy-1,1’-binaphthyl as
white crystalline solid; yield: 375 mg (60%). The physical
and spectral data were identical to those previously reported
Revised Synthesis of (S)-3,3’-Di(2-hydroxyphenyl)-
2,2’-dihydroxy-1,1’-binaphthyl [Precursor to the
Catalyst (S)-14]
1
for this compound.[26] [a]23: 153.6 (c 2.50, CHCl3); H NMR
(500 MHz, CDCl3): d=5.D82 (br s, 2H), 6.65 (br s, 2H), 6.86
(t, J=7.5 Hz, 2H), 7.14 (m, 2H), 7.26 (m, 4H), 7.33 (d, J=
7.5 Hz, 2H), 7.57 (d, J=7.0 Hz, 2H), 7.70 (s, 2H), 7.73 (br s,
2H); 13C NMR (125 MHz, CDCl3): d=114.77, 115.96,
120.77, 124.05, 124.36, 124.92, 126.83, 128.04, 128.34, 129.19,
In a 500-mL, flame-dried, three-necked, round-bottomed
flask equipped with an argon inlet were placed dry Et2O
(150 mL) and TMEDA (3.2 g, 27 mmol). To this solution
was added 1.6m n-BuLi in hexane (18 mL, 29 mmol). The
solution was stirred for 30 min at room temperature, solid
2454
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Adv. Synth. Catal. 2006, 348, 2449 – 2456