mp 98.2–98.8 ЊC (from benzene–hexane); [α]D23 ϩ34.0 (c 1.00 in
CHCl3) (Found: C, 78.5; H, 5.8. C34H30O5 requires C, 78.7; H,
5.8%); νmax(KBr)/cmϪ1 2920, 1744, 1678, 1203 and 1142; δH 1.66
(2 H, quintet, J 6.2, OCH2CH2CH2O), 2.35–2.80 (4 H, m,
ArO2CCH2CH2COPh), 2.8–3.0 (2 H, m, CH2OMe), 3.01 (3 H,
s, OMe), 3.98–4.10 (2 H, m, ArOCH2) and 7.19–8.0 (17 H, m,
Ar); δC (CD2Cl2) 28.4, 29.5, 33.2, 58.3, 66.2, 66.7, 115.0, 121.9,
123.7, 125.1, 125.4, 126.2, 126.3, 126.6, 127.8, 128.0, 128.4,
128.8, 129.8, 131.7, 133.2, 133.7, 136.2, 146.3, 154.3, 170.9
(CO2Ar) and 197.3 (PhCO).
(8 H, m, CH2OCH2CH2OCH2CHMe2), 3.99–4.08 (2 H, m,
ArOCH2) and 7.18–7.99 (17 H, m, Ar); δC 19.3, 28.2, 28.4, 29.6,
33.2, 66.3, 67.3, 70.0, 115.0, 121.9, 123.7, 125.1, 125.4, 126.2,
126.3, 126.6, 127.8, 128.0, 128.4, 128.8, 129.0, 129.8, 131.7,
133.1, 133.7, 136.3, 146.7, 154.3, 170.9 (CO2Ar) and 197.3
(PhCO).
(R)-2Ј-{2-[2-(2-Methoxyethoxy)ethoxy]ethoxy}-1,1Ј-binaph-
thalen-2-yl 3-benzoylpropionate 4j. Eluent: 50% ethyl acetate in
benzene; yield 76%; [α]D23 ϩ26.4 (c 1.19 in CHCl3) (Found: C,
74.95; H, 6.2. C37H36O7 requires C, 75.0; H, 6.1%); νmax(film)/
cmϪ1 2875, 1759, 1682, 1206 and 1147; δH 2.35–2.85 (4 H, m,
ArO2CCH2CH2COPh), 3.0–3.50 [10 H, m, CH2O(CH2CH2O)2
Me], 3.32 (3 H, s, OMe), 4.08 (2 H, t, J 4.9, ArOCH2) and 7.15–
8.0 (17 H, m, Ar); δC (CD2Cl2) 28.7, 33.6, 58.9, 69.8, 70.1, 70.5,
70.6, 70.9, 72.2, 115.7, 118.6, 122.4, 124.2, 125.5, 125.9, 126.4,
126.9, 128.3, 128.4, 128.7, 128.8, 129.1, 129.5, 130.4, 132.1,
133.5, 134.0, 136.6, 147.2, 154.8, 171.2 (CO2Ar) and 197.5
(PhCO).
(R)-2Ј-(5-Methoxypentyloxy)-1,1Ј-binaphthalen-2-yl 3-benz-
oylpropionate 4e. Eluent: 10% ethyl acetate in benzene (for both
alumina and silica); yield 90%; [α]D20 ϩ25 (c 0.39 in CHCl3)
(Found: C, 79.4; H, 6.3. C36H34O5 requires C, 79.1; H, 6.3%);
νmax(film)/cmϪ1 3056, 1759, 1686, 1246, 1210, 1139 and 1082;
δH 0.9–1.0 (2 H, m, CH2CH2OMe), 1.2–1.3 (2 H, m, ArO-
CH2CH2), 1.35–1.45 (2 H, m, ArOCH2CH2CH2CH2CH2OMe),
2.35–2.8 (4 H, m, ArO2CCH2CH2COPh), 3.0–3.1 (2 H, m,
CH2OMe), 3.20 (3 H, s, OMe), 3.85–3.97 (2 H, m, ArOCH2)
and 7.15–8.0 (17 H, m, Ar); δC 22.0, 28.4, 28.9, 33.2, 58.4, 69.4,
72.5, 115.2, 118.5, 121.8, 123.7, 125.1, 125.4, 126.2, 126.3,
126.5, 127.7, 128.0, 128.4, 128.8, 128.9, 129.8, 131.7, 133.1,
133.7, 136.1, 146.6, 154.4, 170.9 (CO2Ar) and 197.3 (PhCO).
(R)-2Ј-(2-Methoxyethoxy)-1,1Ј-binaphthalen-2-yl
4-oxo-
pentanoate 5. Eluent: 17% ethyl acetate in benzene; yield
83%; [α]D21 ϩ44.8 (c 1.21 in CHCl3) (Found: C, 75.8; H, 6.0.
C28H26O5 requires C, 76.0; H, 5.9%); νmax(film)/cmϪ1 2925,
1750, 1718, 1211 and 1137; δH 1.92 (3 H, s, COMe), 2.12–2.41
(4 H, m, ArO2CCH2CH2COMe), 2.99 (3 H, s, OMe), 3.27–3.40
(2 H, m, CH2OMe), 4.06 (2 H, t, J 5.0, ArOCH2) and 7.16–
7.99 (12 H, m, Ar); δC (CD2Cl2) 28.3, 29.5, 37.9, 59.0, 69.9,
71.3, 116.0, 118.7, 122.3, 124.2, 125.6, 125.8, 126.4, 126.7,
126.8, 128.2, 128.4, 129.1, 129.6, 130.3, 132.0, 134.0, 147.2,
154.9, 171.1 (CO2Ar) and 206.0 (MeCO).
(R)-2Ј-(2-Methoxyethoxy)methoxy-1,1Ј-binaphthalen-2-yl 3-
benzoylpropionate 4f. Eluent: 30% ethyl acetate in hexane; yield
69%; [α]D23 ϩ54.7 (c 1.05 in THF) (Found: C, 76.6; H, 6.0.
C34H30O6 requires C, 76.4; H, 5.7%); νmax(film)/cmϪ1 2920, 1759,
1687, 1209 and 1137; δH 2.4–2.75 (4 H, m, ArO2CCH2CH2-
COPh), 3.25–3.55 (4 H, m, CH2CH2OMe), 3.25 (3 H, s, OMe),
5.06 and 5.12 (2 H, ABq, J 7.2, ∆ν 5.4, OCH2O) and 7.13–8.00
(17 H, m, Ar); δC 28.4, 33.2, 58.8, 67.4, 71.3, 93.9, 116.4, 119.1,
121.9, 124.2, 124.9, 125.5, 126.1, 126.4, 126.6, 127.7, 128.0,
128.1, 128.3, 128.4, 129.1, 129.5, 129.9, 131.7, 133.2, 133.6,
136.1, 146.7, 152.7, 171.0 (CO2Ar) and 197.2 (PhCO).
(R)-2Ј-[2-(2-Methoxyethoxy)ethoxy]-1,1Ј-binaphthalen-2-yl
4-oxopentanoate 6. Eluent: 10% ethyl acetate in benzene; yield
69%; [α]D24 ϩ32.6 (c 1.30 in CHCl3) (Found: C, 73.8; H, 6.2.
C30H30O6 requires C, 74.05; H, 6.2%); νmax(film)/cmϪ1 2876,
1757, 1715, 1211 and 1139; δH 1.90 (3 H, s, COMe), 2.1–2.4
(4 H, m, ArO2CCH2CH2COMe), 3.20 (3 H, s, OMe), 3.0–3.15
and 3.4–3.6 (6 H, m, CH2OCH2CH2OMe), 4.10 (2 H, t, J 4.8,
ArOCH2) and 7.1–8.0 (12 H, m, Ar); δC 28.0, 29.5, 37.6, 58.8,
69.4, 69.8, 70.4, 71.6, 115.0, 118.3, 121.8, 123.8, 125.0, 125.4,
125.5, 126.2, 126.4, 126.6, 127.8, 128.0, 128.8, 129.1, 129.9,
131.6, 133.7, 146.7, 154.3, 170.8 (CO2Ar) and 205.9 (MeCO).
(R)-2Ј-[2-(2-Methoxyethoxy)ethoxy]-1,1Ј-binaphthalen-2-yl
3-benzoylpropionate 4g. Eluent: 20% ethyl acetate in benzene;
yield 93%; [α]D20 ϩ31.8 (c 1.01 in MeOH) (Found: C, 76.9; H, 6.1.
C35H32O6 requires C, 76.6; H, 5.9%); νmax(film)/cmϪ1 2910, 1758,
1685, 1204 and 1138; δH 2.35–2.85 (4 H, m, ArO2CCH2-
CH2COPh), 2.95–3.15 (4 H, m, OCH2CH2OMe), 3.20 (3 H, s,
OMe), 3.4–3.55 (2 H, m, ArOCH2CH2O), 4.10 (2 H, t, J 6.2,
ArOCH2) and 7.15–7.95 (17 H, m, Ar); δC (CD2Cl2) 28.7, 33.6,
58.8, 70.1, 70.8, 72.0, 115.6, 118.8, 122.4, 124.2, 125.3, 125.6,
125.9, 126.4, 126.7, 126.8, 128.3, 128.5, 128.9, 129.2, 129.6,
130.4, 132.1, 133.6, 134.0, 147.2, 155.0, 171.3 (CO2Ar) and
197.6 (PhCO).
(R)-2Ј-(2-Methoxyethoxy)-1,1Ј-binaphthalen-2-yl 5-methyl-4-
oxohexanoate 7. Eluent: 10% ethyl acetate in benzene; yield
98%; [α]D10 ϩ36.9 (c 1.00 in CHCl3) (Found: C, 76.9; H, 6.5.
C30H30O5 requires C, 76.6; H, 6.4%); νmax(film)/cmϪ1 2970, 1759,
1713, 1212 and 1144; δH 0.96 and 0.97 (each 3 H, d, J 6.9,
CHMe2), 2.12–2.41 (5 H, m, ArO2CCH2CH2COCHMe2), 2.98
(3 H, s, OMe), 3.25–3.40 (2 H, m, CH2OMe), 4.06 (2 H, t, J 5.1,
ArOCH2) and 7.16–7.98 (12 H, m, Ar); δC 18.1, 28.0, 34.4, 40.5,
58.9, 69.9, 70.9, 115.8, 118.8, 121.8, 123.9, 124.9, 125.4, 125.5,
126.2, 126.3, 126.5, 127.7, 127.9, 128.3, 128.9, 129.2, 129.9,
131.6, 133.6, 133.7, 146.7, 154.4, 171.0 (CO2Ar) and 212.0
(PriCO).
(R)-2Ј-[3-(2-Methoxyethoxy)propoxy]-1,1Ј-binaphthalen-2-yl
3-benzoylpropionate 4h. Eluent: 40–50% ethyl acetate in hexane
(gradient); yield 74%; [α]D20 ϩ25.2 (c 0.99 in CHCl3) (Found: C,
76.8; H, 6.2. C36H34O6 requires C, 76.85; H, 6.1%); νmax(film)/
cmϪ1 2920, 1759, 1687, 1211 and 1140; δH 1.6–1.8 (2 H, m,
OCH2CH2CH2O), 2.35–2.80 (4 H, m, ArO2CCH2CH2COPh),
2.9–3.4 (6 H, m, CH2OCH2CH2O), 3.29 (3 H, s, OMe), 3.95–
4.15 (2 H, m, ArOCH2) and 7.2–8.0 (17 H, m, Ar); δC 28.3, 29.4,
33.1, 58.9, 66.1, 67.3, 69.7, 71.6, 114.9, 118.2, 121.6, 123.7,
125.0, 125.3, 126.1, 126.2, 126.5, 127.7, 127.9, 128.2, 128.4,
128.7, 128.9, 129.8, 131.6, 133.1, 133.6, 136.1, 146.6, 154.2,
170.8 (CO2Ar) and 197.2 (PhCO).
2-Naphthyl 3-benzoylpropionate 15. Eluent: 10% ethyl acetate
in benzene; yield 89%; mp 99.6–100.1 ЊC (from benzene–
hexane) (Found: C, 79.15; H, 5.5. C20H16O3 requires C, 78.9;
H, 5.3%); νmax(KBr)/cmϪ1 1752, 1680, 1210 and 1149; δH 3.08
(2 H, t, J 6.5, ArO2CCH2), 3.47 (2 H, t, J 6.5, CH2COPh) and
7.24–8.05 (12 H, m, Ar); δC (CD2Cl2) 28.8 (CH2CO2Ar), 33.9
(PhCOCH2), 116.8, 121.6, 126.1, 126.9, 127.9, 128.1, 128.3,
129.0, 129.6, 131.8, 133.6, 134.1, 136.9, 148.9, 172.1 (CO2Ar)
and 198.2 (PhCO).
(R)-2Ј-[3-(2-Isobutoxyethoxy)propoxy]-1,1Ј-binaphthalen-2-
yl 3-benzoylpropionate 4i. Eluent: 10% ethyl acetate in benzene;
yield 90%; [α]D20 ϩ20.6 (c 1.00 in CHCl3) (Found: C, 77.2; H, 6.7.
C39H40O6 requires C, 77.5; H, 6.7%); νmax(film)/cmϪ1 2950, 1760,
1688, 1211 and 1140; δH 0.86 (6 H, d, J 6.5, CHMe2), 1.68 (2 H,
quintet, J 6.1, OCH2CH2CH2O), 1.82 (1 H, septet, J 6.5,
CHMe2), 2.35–2.80 (4 H, m, ArO2CCH2CH2COPh), 2.96–3.38
Representative procedure for the DIBAL-H reductions (Table 2,
run 7)
To a stirred solution of the keto ester 4h (54 mg, 0.096 mmol) in
J. Chem. Soc., Perkin Trans. 1, 1999, 1685–1694
1691