5562 J . Org. Chem., Vol. 61, No. 16, 1996
Cimarelli and Palmieri
1
IR (film) 3330, 1720, 1150 cm-1; H NMR δ 0.79 (s, 9H), 1.25
6.6 Hz), 5.17 and 5.23 (two d, 2H, J AB ) 11.5 Hz), 7.23-7.49
(m, 10 H); 13C NMR δ 22.5, 25.2, 28.5, 32.9, 47.0, 57.1, 60.8,
66.6, 127.1, 127.2, 128.7, 128.8, 129.0, 129.1, 136.7, 146.4,
175.4; MS m/e 323 (M+, 1), 308 (83),105 (100). Anal. Calcd
for C21H25NO2: C, 77.99; H, 7.79; N, 4.33. Found: C, 77.73;
H, 7.55; N, 4.18.
(t, 3H, J ) 7.2 Hz), 1.30 (d, 3H, J ) 6.4 Hz), 1.40 (br s, 1H),
2.27 (dd, 1H, J ) 13.7, 4.6 Hz), 2.51 (t, 1H, J ) 5.0 Hz), 2.56
(dd, 1H, J ) 13.7, 5.5 Hz), 3.80 (q, 1H, J ) 6.5 Hz), 4.12 (q,
2H, J ) 7.2 Hz), 7.18-7.35 (m, 5H); 13C NMR δ 14.1, 25.0,
26.6, 35.1, 36.3, 56.1, 60.3, 60.8, 126.7, 127.3, 128.0, 145.8,
174.2; MS m/z 277 (M+, 1), 262 (1), 220 (50), 105 (100). Anal.
Calcd for C17H27NO2: C, 73.61; H, 9.81; N, 5.05. Found: C,
73.52; H, 9.98; N, 5.18.
(R,R,R)-1-[N-(r-Meth ylben zyl)a m in o]-2-m eth yl-3-ca r -
beth oxyp yr r olid in e [(R,R,R)-2k ]: oil; [R]20 +31.1 (c 4.2,
D
EtOH); IR (neat) 1735, 1170 cm-1; 1H NMR δ 0.82 (d, 3H, J )
6.4 Hz), 1.26 (t, 3H, J ) 7.1 Hz), 1.35 (d, 3H, J ) 6.5 Hz),
1.78-3.26 (m, 5H), 3.42-3.70 (m, 2H), 4.14 (q, 2H, J ) 7.1
Hz), 7.20-7.40 (m, 5H); 13C NMR δ 13.0, 14.8, 21.4, 25.3, 48.0,
49.3, 57.5, 60.8, 61.3, 127.4, 127.9, 128.7, 145.8, 173.6; MS m/z
261 (M+, 10), 246 (100), 142 (77). Anal. Calcd for C16H23NO2:
C, 73.53; H, 8.87; N, 5.36. Found: C, 73.71; H, 8.95; N, 5.19.
(R,R,R)-1-[N-(r-Meth ylben zyl)a m in o]-2-m eth yl-3-ca r -
bom eth oxyp yr r olid in e [(R,R,R)-2l]: oil; [R]20D +27.2 (c 2.9,
(R,R)-Eth yl 3-(N-(r-m eth ylben zyl)a m in o]-3-p h en ylp r o-
p a n oa te [(R,R)-2e]: oil; [R]20 +84.5 (c 3.6, EtOH); IR (film)
D
3340, 1735, 1180 cm-1; H NMR δ 1.20 (t, 3H, J ) 7.14 Hz),
1
1.28 (d, 3H, J ) 6.7 Hz), 2.18 (br s, 1H), 2.53 (dd, 1H, J )
15.2, 5.3 Hz), 2.65 (dd, 1H, J ) 15.2, 9.0 Hz), 3.49 (q, 1H, J )
6.7 Hz), 3.81 (dd, 1H, J ) 9.0, 5.3 Hz), 3.99-4.22 (m, 2H),
7.18-7.39 (m, 10H); 13C NMR δ 14.6, 25.3, 43.5, 55.4, 57.1,
61.0, 127.3, 127.5, 127.7, 127.9, 128.9, 129.0, 142.6, 145.1,
172.1; MS m/z 297 (M+, 1), 282 (45), 210 (67), 105 (100). Anal.
Calcd for C19H23NO2: C, 76.74; H, 7.80; N, 4.71. Found: C,
76.56; H, 7.58; N, 4.46.
1
EtOH); IR (neat) 3300, 1715, 1155 cm-1; H NMR δ 0.80 (d,
3H, J ) 6.4 Hz), 1.35 (d, 3H, J ) 6.5 Hz), 1.80-3.60 (m, 7H),
3.67 (s, 3H), 7.18-7.39 (m, 5H); 13C NMR δ 12.5, 20.9, 24.9,
47.4, 48.8, 51.5, 56.9, 60.7, 126.8, 127.4, 128.2, 145.3, 173.7;
(2S,3R,rR)-Eth yl 3-[N-(r-m eth ylben zyl)a m in o]-2-m eth -
ylbu ta n oa te [(2S,3R,rR)-2f]: oil; [R]20D +46.3 (c 1.8, EtOH);
MS m/z 247 (M+, 5), 232 (100), 105 (57). Anal. Calcd for C15
-
1
IR (film) 3350, 1735, 1190 cm-1; H NMR δ 0.98 (d, 3H, J )
H21NO2: C, 72.84; H, 8.56; N, 5.66. Found: C, 72.97; H, 8.78;
N, 5.44.
6.6 Hz), 1.09 (d, 3H, J ) 6.9 Hz), 1.28 (t, 3H, J ) 7.0 Hz), 1.30
(d, 3H, J ) 6.5 Hz), 1.43 (br s, 1H), 2.69 (qd, 1H, J ) 6.9, 4.4
Hz), 2.74 (qd, 1H, J ) 6.6, 4.4 Hz), 3.94 (q, 1H, J ) 6.5 Hz),
4.16 (q, 2H, J ) 7.0 Hz), 7.17-7.35 (m, 5H); 13C NMR δ 13.8,
14.8, 18.6, 25.2, 43.3, 53.5, 55.5, 60.6, 127.1, 127.3, 128.9, 146.7,
175.6; MS m/z 249 (M+, 1), 234 (32), 148 (97), 105 (100). Anal.
Calcd for C15H23NO2: C, 72.25; H, 9.30; N, 5.62. Found: C,
72.43; H, 9.42; N, 5.37.
(3S,1′R,rR)-Dih yd r o-3-[1′-[N-(r-m eth ylben zyl)a m in o)-
eth yl]-2(3H)-fu r an on e [(3S,1′R,rR)-2m ]: mp 61-63 °C (CH2-
Cl2-hexane); [R]20D +44.2 (c 4.9, EtOH); IR (Nujol) 3320, 1750,
1160 cm-1; 1H NMR δ 1.02 (d, 3H, J ) 6.7 Hz), 1.30 (d, 3H, J
) 6.5 Hz), 1.47 (br s, 1H), 2.08-2.33 (m, 2H), 2.69 (td, 1H, J
) 9.1, 3.4 Hz), 3.09 (qd, 1H, J ) 6.7, 3.4 Hz), 3.87 (q, 1H, J )
6.5 Hz), 4.24 (dt, 1H, J ) 8.7, 7.8 Hz), 4.36 (td, 1H, J ) 7.8,
5.5 Hz), 7.18-7.35 (m, 5H); 13C NMR δ 19.2, 23.9, 24.5, 43.8,
50.3, 55.7, 67.0, 126.5, 126.9, 128.4, 146.3, 178.7; MS m/z 233
(M+, 1), 218 (55), 148 (26), 120 (36), 105 (100). Anal. Calcd
for C14H19NO2: C, 72.07; H, 8.21; N, 6.00. Found: C, 72.19;
H, 8.34; N, 5.82.
(2S,3R,rR)-Meth yl 3-[N-(r-m eth ylben zyl)am in o]-2-m eth -
ylbu ta n oa te [(2S,3R,rR)-2g]: oil; [R]20D +47.4 (c 3.8, EtOH);
1
IR (film) 3320, 1725, 1190 cm-1; H NMR δ 0.97 (d, 3H, J )
6.5 Hz), 1.09 (d, 3H, J ) 6.9 Hz), 1.30 (d, 3H, J ) 6.5 Hz),
1.45 (br s, 1H), 2.70 (qd, 1H, J ) 6.9, 4.5 Hz), 2.75 (qd, 1H, J
) 6.5, 4.5 Hz), 3.70 (s, 3H), 3.91 (q, 1H, J ) 6.5 Hz), 7.15-
7.33 (m, 5H); 13C NMR δ 13.2, 18.2, 24.6, 43.1, 51.3, 53.0, 55.1,
126.5, 126.8, 128.3, 146.3, 175.6; MS m/z 235 (M+, 1), 220 (14),
148 (72), 105 (100). Anal. Calcd for C14H21NO2: C, 71.56; H,
8.99; N, 5.95. Found: C, 71.68; H, 9.21; N, 5.82.
(R,R,R)-Dih ydr o-3-[1′-[N-(r-m eth ylben zyl)am in o]eth yl]-
2(3H)-fu r a n on e [(R,R,R)-2m ]: mp 69-70 °C (CH2Cl2-hex-
ane); [R]20 +34.1 (c 1.6, EtOH); IR (Nujol) 3310, 1735, 1170
D
cm-1; 1H NMR δ 0.94 (d, 3H, J ) 6.4 Hz), 1.26 (d, 3H, J ) 6.5
Hz), 1.60 (br s, 1H), 2.01-2.22 (m, 2H), 2.70 (td, 1H, J ) 9.5,
5.2 Hz), 3.00 (qd, 1H, J ) 6.4, 5.2 Hz), 3.76 (q, 1H, J ) 6.5
Hz), 4.07 (td, 1H, J ) 8.8, 7.6 Hz), 4.21 (td, 1H, J ) 8.5, 4.1
Hz), 7.12-7.31 (m, 5H); 13C NMR δ 17.7, 23.8, 24.4, 43.3, 50.6,
55.3, 66.8, 126.4, 126.9, 128.4, 146.0, 178.6; MS m/z 233 (M+,
(1S,2R,rR)-2-[N-(r-Meth ylben zyl)am in o]-1-car beth oxy-
cycloh exa n e [(1S,2R,rR)-2h ]: oil; [R]20D +59.5 (c 2.8, EtOH);
IR (neat) 3340, 1720, 1175 cm-1; H NMR δ 1.27 (d, 3H, J )
1
6.5 Hz), 1.30 (t, 3H, J ) 7.1 Hz), 1.35-1.95 (m, 9H), 2.70-
2.88 (m, 2H), 3.87 (q, 1H, J ) 6.5 Hz), 4.19 (q, 2H, J ) 7.1
Hz), 7.15-7.37 (m, 5H); 13C NMR δ 14.9, 23.3, 23.8, 25.1, 26.0,
30.4, 45.0, 53.9, 55.5, 60.4, 127.1, 127.2, 128.8, 147.0, 175.0;
MS m/z 275 (M+, 2), 260 (65), 120 (55), 105 (100). Anal. Calcd
for C17H25NO2: C, 74.14; H, 9.15; N, 5.09. Found: C, 73.91;
H, 9.28; N, 5.27.
1), 218 (67), 148 (17), 120 (51), 105 (100). Anal. Calcd for C14
-
H19NO2: C, 72.07; H, 8.21; N, 6.00. Found: C, 72.13; H, 8.38;
N, 5.78.
Hyd r ogen olysis of â-[N-r-Meth ylben zyl)a m in o] Ester s
2 to â-Am in o Ester s 3. Gen er a l P r oced u r e. The â-amino
ester 2 (3 mmol) in MeOH (20 mL), water (2 mL), and CH3-
COOH (0.5 mL) in the presence of palladium hydroxide on
charcoal (20%, 0.2 g) was placed under hydrogen (3 atm) and
stirred at rt overnight. Then the solution was partitioned
between Na2CO3 (saturated acqueous solution, 20 mL) and
CH2Cl2 (100 mL) and the organic phase dried (Na2SO4) and
filtered through a plug of Celite to provide the pure â-amino
ester 3 in high yield after evaporation of the solvent.
Eth yl (3S)-3-a m in oh exa n oa te [(3S)-3b]: yield 86%; oil;
[R]20D) -10.7 (c 2.1, H2O); IR (neat) 1450, 1190 cm-1; 1H NMR
δ 0.89 (m, 3H), 1.21 (t, 3H, J ) 7.2 Hz), 1.34 (m, 4H), 1.59 (br
s, 2H), 2.19 (dd, 1H, J ) 15.6, 8.8 Hz), 2.41 (dd, 1H, J ) 15.6,
4.0 Hz), 3.13 (m, 1H), 4.10 (q, 2H, J ) 7.2 Hz); 13C NMR δ
13.9, 14.2, 19.1, 39.7, 42.6, 47.9, 60.2, 172.6; MS m/z 159 (M+,
1), 130 (5), 116 (100). Anal. Calcd for C8H17NO2: C, 60.35;
H, 10.76; N, 8.80. Found: C, 60.48; H, 10.93; N, 8.92.
Eth yl (3S)-3-a m in o-4-m eth ylp en ta n oa te [(3S)-3c]: yield
81%; oil; [R]20D ) -26.2 (c 2.3, H2O); IR (neat) 3360, 1720, 1160
cm-1; 1H NMR δ 0.89 (d, 3H, J ) 6.8 Hz), 0.90 (d, 3H, J ) 6.8
Hz), 1.24 (t, 3H, J ) 7.1 Hz), 1.43 (br s, 2 H), 1.60 (sept d, 1H,
J ) 6.8, 5.1 Hz), 2.19 (dd, 1H, J ) 15.5, 9.7 Hz), 2.43 (dd, 1H,
J ) 15.5, 3.5 Hz), 3.00 (ddd, 1H, J ) 9.7, 5.1, 3.5 Hz), 4.13 (q,
2H, J ) 7.1 Hz); 13C NMR δ 14.2, 17.7, 18.7, 33.4, 39.8, 53.5,
60.3, 173.0; MS m/z 159 (M+, 2), 144 (3), 116 (100). Anal. Calcd
for C8H17NO2: C, 60.35; H, 10.76; N, 8.80. Found: C, 60.39;
H, 10.89; N, 8.67.
(R,R,R)-2-[N-(r-Meth ylben zyl)a m in o]-1-ca r beth oxycy-
cloh exa n e [(R,R,R)-2h ]: oil; [R]20 -72.1 (c 2.1, EtOH); IR
D
(neat) 3340, 1720, 1175 cm-1; H NMR δ 1.26 (d, 3H, J ) 6.5
1
Hz), 1.30 (t, 3H, J ) 7.2 Hz), 0.80-1.95 (m, 9H), 2.15 (ddd,
1H, J ) 11.7, 10.2, 3.6 Hz), 2.73 (td, 1H, J ) 10.2, 3.9 Hz),
3.83 (q, 1H, J ) 6.5 Hz), 4.19 (q, 2H, J ) 7.2 Hz), 7.15-7.37
(m, 5H); 13C NMR δ 14.8, 24.4, 25.4, 25.5, 29.7, 33.8, 52.3, 56.2,
56.6, 60.6, 127.0, 127.2, 128.8, 147.6, 176.2; MS m/z 275 (M+,
2), 260 (58), 120 (53), 105 (100). Anal. Calcd for C17H25NO2:
C, 74.14; H, 9.15; N, 5.09. Found: C, 73.94; H, 9.32; N, 4.87.
(1S,2R,rR)-2-[N-(r-Meth ylben zyl)a m in o]-1-ca r beth oxy-
cyclop en ta n e [(1S,2R,rR)-2i]: oil; [R]20 +101.6 (c 4.1,
D
EtOH); IR (neat) 3350, 1730, 1190 cm-1; H NMR δ 1.27 (d,
1
3H, J ) 6.6 Hz), 1.32 (t, 3H, J ) 7.1 Hz), 1.40-2.05 (m, 7H),
2.93 (td, 1H, J ) 7.3, 4.8 Hz), 3.02-3.16 (m, 1H), 3.83 (q, 1H,
J ) 6.6 Hz), 4.20 (q, 2H, J ) 7.1 Hz), 7.17-7.35 (m, 5H); 13C
NMR δ 14.3, 22.0, 24.9, 27.9, 32.5, 46.4, 56.6, 60.1, 60.2, 126.6,
126.7, 128.3, 146.0, 175.1; MS m/z 261 (M+, 1), 246 (85), 120
(64), 105 (100). Anal. Calcd for C16H23NO2: C, 73.53; H, 8.87;
N, 5.36. Found: C, 73.71; H, 8.99; N, 5.19.
(1S ,2R ,rR )-2-[N -(r-Me t h ylb e n zyl)a m in o]-1-(ca r b o-
ben zoxy)cyclop en ta n e [(1S,2R,rR)-2j]: oil; [R]20 +73.9 (c
D
2.3, EtOH); IR (neat) 3300, 1720, 1150 cm-1; H NMR δ 1.15
1
(d, 3H, J ) 6.6 Hz), 1.35-2.10 (m, 6H), 2.20 (br s, 1H), 3.00
(td, 1H, J ) 7.3, 4.4 Hz), 3.07-3.19 (m, 1H), 3.75 (q, 1H, J )