acid (697 mg, 3.0 mmol), to the mixture was added dropwise
for ca. 20 min 1-naphthaldehyde (8; 17.2 g, 110 mmol) in
toluene (5 mL). After stirring at the same temperature for 1
h, the mixture was seeded with material (>∼90% de) from
a small-scale preparation. After ∼30 min, white precipitates
of the desired product 9a gradually appeared and increased.
The slurry was stirred at that temperature for 3 h, and it was
with water and brine, dried (Na
obtained crude oil (92% de based on H NMR measurement)
was purified by SiO -column chromatography (hexane-
AcOEt ) 30:1 to 20:1) to give (2S,5S)-5-methyl-2-(1-
naphthyl)-5-phenyl-1,3-dioxolan-4-one (10; 6.20 g, 79%,
2 4
SO ), and concentrated. The
1
2
92% de).
Colorless liquid; [R]25
+64.4 (c 1.21, CHCl
); H NMR
1
D
3
quenched with saturated NaHCO
was extracted twice with AcOEt. The combined organic
phase was washed with water and brine, dried (Na SO ), and
3
aqueous solution, which
(300 MHz, CDCl
(dd, 1H, J ) 7.2, 8.3 Hz), 7.51-7.62 (m, 4H), 7.70-7.77
3
) δ 1.97 (s, 1H), 7.22-7.35 (m, 4H), 7.44
13
2
4
(m, 1H), 7.85-7.95 (m, 2H), 8.09-8.20 (m, 1H); C NMR
(75 MHz, CDCl ) δ 23.69, 79.98, 99.83, 123.21, 124.00,
concentrated. The obtained crude product (92% de based on
3
1
H NMR measurement) was collected, using a glass filter,
124.96, 124.99, 126.16, 126.92, 128.26, 128.36, 128.82,
washing with 100 mL of hexanes-Et
crude solid was purified by recrystallization from AcOEt (ca.
0 mL) to give 9a (21.4 g, 74%, >99% de).
2
O (2:1). The resultant
130.25, 130.42, 130.69, 133.64, 138.99, 173.73; IR (KBr)
-1
3063, 2978, 2932, 1795, 1217, 1132, 966 cm ; HRMS (ESI)
+
3
calcd for C20H O
16 3
(M + Na ) 327.0997, found 327.1001.
25
Colorless crystals; mp 132-133 °C; [R]
D
+65.5 (c 0.99,
) δ 5.54 (s, 1H), 7.25
s, 1H), 7.35-7.45 (m, 3H), 7.45-7.62 (m, 5H), 7.88-7.99
(2S,5S)-5-Benzyl-2-(1-naphthyl)-5-phenyl-1,3-dioxolan-
1
25
CHCl
3
); H NMR (300 MHz, CDCl
3
4-one (11): colorless crystals; mp 101-104 °C; [R]
(c 1.02, CHCl ); H NMR (300 MHz, CDCl
3 3
D
+15.5
) δ 3.33 (d,
1H, J ) 13.8 Hz), 3.68 (d, 1H, J ) 13.8 Hz), 6.34 (s, 1H),
1
(
(
13
m, 3H), 8.09-8.16 (m, 1H); C NMR (75 MHz, CDCl
3
) δ
1
3
7
1
1
9
3
7.13, 101.30, 123.08, 124.11, 125.05, 126.24, 127.06,
7.25-7.89 (m, 17H); C NMR (75 MHz, CDCl ) δ 45.91,
3
27.10, 128.80, 128.86, 129.32, 129.68, 130.46, 131.00,
33.35, 133.64, 171.29; IR (KBr) 1786, 1244, 1211, 1159,
83.79, 101.04, 123.08, 123.43, 124.94, 124.99, 126.05,
126.79, 127.75, 129.32, 128.21, 128.34, 128.72, 130.25,
130.44, 130.54, 130.71, 133.52, 134,57, 138.72, 173.12; IR
-1
+
41, 783 cm ; HRMS (ESI) calcd for C19
14 3
H O (M + Na )
-
1
13.0841, found 313.0843.
(KBr) 3061, 3030, 1804, 1784, 1182 cm ; HRMS (ESI)
+
(
2R,5R)-5-(3-Chlorophenyl)-2-(1-naphthyl)-1,3-dioxolan-
calcd for C26H O
20 3
(M + Na ) 403.1310, found 403.1301.
25
4
(
-one (9b): colorless crystals; mp 105-110 °C; [R]
c 1.02, CHCl
D
-79.9
) δ 5.49 (s, 1H),
(2S,5S)-2-(1-Naphthyl)-5-phenyl-5-(2-propenyl)-1,3-di-
1
25
3
); H NMR (300 MHz, CDCl
3
oxolan-4-one (12): colorless crystals; mp 96-99 °C; [R]
D
1
7
8
.22 (s, 1H), 7.26-7.41 (m, 3H); 7.45-7.62 (m, 4H), 7.82-
3 3
+63.7 (c 1.33, CHCl ); H NMR (300 MHz, CDCl ) δ2.91
.00 (m, 3H), 8.05-8.14 (m, 1H); 13C NMR (75 MHz,
(dd, 1H, J ) 7.2, 14.5 Hz), 3.68 (dd, 1H, J ) 6.8, 14.4 Hz),
5.24-5.40 (m, 2H), 5.85-6.04 (m, 1H), 7.17-7.47 (m, 4H),
7.47-7.68 (m, 5H), 7.84-7.94 (m, 2H), 8.07-8.17 (m, 1H);
CDCl
3
) δ 76.18, 101.49, 122.97, 124.09, 124.97, 125.03,
26.29, 126.98, 127.10, 128.89, 129.35, 129.41, 130.04,
30.37, 131.13, 133.64, 134.73, 135.13, 170.62; IR (KBr)
1
1
3
1
3
C NMR (75 MHz, CDCl ) δ 43.33, 82.53, 100.90, 121.06,
3
-
1
063, 2949, 1788, 1412, 1206 cm ; HRMS (ESI) calcd for
121.18, 123.24, 123.66, 124.92, 125.03, 126.12, 126.91,
128.13, 128.23, 128.80, 130.33, 130.54, 130.79, 133.62,
137.88, 172.89; IR (KBr) 3067, 2913, 1346, 1206, 1105
+
C
19
H
13ClO
3
(M + Na ) 347.0451, found 347.0455.
(
2R,5R)-5-(4-Chlorophenyl)-2-(1-naphthyl)-1,3-dioxolan-
25
-1
+
4
(
-one (9c): colorless crystals; mp 105-109 °C; [R]
c 1.61, CHCl
D
-87.1
) δ 5.50 (s, 1H),
18 3
cm ; HRMS (ESI) calcd for C22H O (M + Na ) 353.1154,
1
3
); H NMR (300 MHz, CDCl
3
found 353.1150.
7
8
.23 (s, 1H), 7.32-7.46 (m, 4H); 7.48-7.64 (m, 3H), 7.80-
(2S,5S)-5-Butyl-2-(1-naphthyl)-5-phenyl-1,3-dioxolan-
.01 (m, 3H), 8.06-8.15 (m, 1H); 13C NMR (75 MHz,
4-one (13): colorless liquid; [R]
25
+64.2 (c 1.00, CHCl
D
3
);
1
CDCl
3
) δ 76.31, 101.48, 122.99, 124.06, 125.031, 126.29,
27.10, 128.25, 128.90, 129.91, 129.22, 129.43, 130.37,
31.11, 133.64, 135.30, 70.90; IR (KBr) 3063, 2946, 1788,
H NMR (300 MHz, CDCl ) δ 0.82-0.99 (m, 3H), 1.17-
3
1
1
1
1.67 (m, 4H), 2.09-2.38 (m, 2H); 7.19-7.27 (m, 3H), 7.32
(s, 1H), 7.37-7.75 (m, 6H), 7.85-8.05 (m, 2H), 8.13-08.19
-1
13
491, 1208, 941 cm ; Anal. Calcd for C19
3
H13ClO : C, 70.3;
(m, 1H); C NMR (75 MHz, CDCl
3
) δ 13.90, 22.60, 25.85,
H, 4.0, found: C, 70.0; H, 3.8.
Typical Procedure for the Trans Selective Alkylation
of 9a with CH I. BuLi (1.58 M in hexane, 19.7 mL, 31.1
mmol) was added to a stirred solution of Pr
3.7 mmol) in THF (15 mL) at -10 °C under an Ar
atmosphere, and the mixture was stirred at the same
temperature for 30 min. After cooling the mixture to -78
38.16, 82.68, 100.56, 123.27, 123.77, 124.92, 125.01, 126.12,
126.89, 127.92, 128.15, 128.82, 130.37, 130.52, 130.90,
133.64, 138.05, 173.54; IR (KBr) 3063, 2959, 2870, 1794,
1196 cm ; HRMS (ESI) calcd for C23H O (M + Na )
22 3
369.1467, found 369.1468.
3
i
-1
+
2
NH (3.41 g,
3
(2S,5S)-5-(2-Ethoxycarbonylethyl)-2-(1-naphthyl)-5-
2
5
phenyl-1,3-dioxolan-4-one (14): colorless liquid; [R]
D
1
°
C, a solution of 9a (7.53 g, 26.0 mmol) in THF (25 mL)
was slowly added to the mixture, which was stirred at the
same temperature for 30 min. A solution of CH I (7.37 g,
1.9 mmol) in THF (5 mL) was slowly added to the mixture,
3 3
+69.3 (c 1.23, CHCl ); H NMR (300 MHz, CDCl ) δ 1.23
(t, 3H), 2.29-2.58 (m, 3H), 2.66-2.81 (m, 1H), 4.13 (q,
2H, J ) 7.2 Hz), 7.22-7.29 (m, 3H), 7.33 (s, 1H), 7.38-
3
5
7.68 (m, 6H), 7.87-7.94 (m, 2H), 8.11-8.17 (m, 1H); 13
C
which was stirred at the same temperature for 5 min, and
then warmed to 0-5 °C during about 2.5 h. The mixture
was quenched with water (200 mL), which was extracted
twice with ether. The combined organic phase was washed
3
NMR (75 MHz, CDCl ) δ 14.15, 28.80, 32.45, 60.73, 81.61,
100.42, 132.26, 123.94, 124.90, 125.13, 126.18, 126.95,
128.30, 128.34, 128.82, 130.37, 130.43, 130.69, 133.62,
136.68, 172.55, 172.82; IR (KBr) 2982, 2932, 1796, 1732,
Vol. 10, No. 3, 2006 / Organic Process Research & Development
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