δ 7.25 (m, 1H), 7.11 (m, 2H), 6.98 (m, 1H), 4.24 (br m, 2H), 2.79
t, J ) 12.4 Hz, 2H), 2.62 (tt, J ) 12.4, 3.6 Hz, 1H), 2.49 (s, 3H),
.81 (d, J ) 13.0 Hz, 2H), 1.62 (qd, J ) 13.0, 4.4 Hz, 2H), 1.49
ter t-Bu t yl 4-[4-(t r iflu or om et h yl)p h en yl]p ip er id in e-1-
ca r boxyla te (13): colorless oil; 84% assay yield; NMR H 7.57
1
(
1
(
(d, J ) 8.0 Hz, 2H), 7.31 (d, J ) 8.0 Hz, 2H), 4.27 (br m, 2H),
2.82 (t, J ) 12.4 Hz, 2H), 2.72 (tt, J ) 12.4, 3.6 Hz, 1H), 1.83 (d,
J ) 12.8 Hz, 2H), 1.63 (qd, J ) 12.8, 4.0 Hz, 2H), 1.49 (s, 9H);
1
3
s, 9H); C 154.7, 146.4, 138.4, 128.9, 125.1, 124.4, 123.5, 79.4,
4.2, 42.6, 33.0, 28.4, 15.7. Anal. Calcd for C17 S: C, 66.41;
H, 8.20; N, 4.56. Found: C, 66.57; H, 8.32; N, 4.55.
4
H25NO
2
1
3
C 154.8, 149.7, 128.6 (q, J CF ) 32.0 Hz), 127.1, 125.4 (q, J CF
3.2 Hz), 124.2 (d, J CF ) 271.5 Hz), 79.6, 44.1, 42.6, 32.9, 28.4.
Anal. Calcd for C17 NO C, 61.99; H, 6.73; N, 4.25.
Found: C, 62.16; H, 6.59; N, 4.29.
)
ter t-Bu tyl 4-[4-(m eth ylth io)p h en yl]p ip er id in e-1-ca r box-
1
yla te (7): white solid; mp 80-81 °C; 90% assay yield; NMR H
H
22
F
3
2
:
δ 7.22 (m, 2H), 7.13 (m, 2H), 4.24 (br m, 2H), 2.79 (t, J ) 12.4),
2
2
1
H), 2.61 (tt, J ) 12.4, 3.6, 1H), 2.47 (s, 3H), 1.80 (d, J ) 12.8,
H), 1.59 (qd, J ) 12.4, 4.0, 2H), 1.49 (s, 9H); 13C 154.7, 154.7,
42.8, 135.9, 127.2, 127.0, 79.3, 44.3, 42.1, 33.1, 28.4, 16.1. Anal.
ter t-Bu tyl 4-(4-m eth ylp h en yl)p ip er id in e-1-ca r boxyla te
1
(
(
14): colorless oil; 66% assay yield; NMR H δ 7.12 (m, 4H), 4.24
m, 2H), 2.80 (td, J ) 13.0, 2.4 Hz, 2H), 2.61 (tt, J ) 12.0, 3.6
Calcd for C17
6.51; H,8.25, N, 4.39.
ter t-Bu t yl 4-[4-(et h oxyca r b on yl)p h en yl]p ip er id in e-1-
ca r boxyla te (8): colorless oil; 97% assay yield; NMR 1H 7.97
2
H25NO S: C, 66.41; H, 8.20; N, 4.56. Found: C,
Hz, 1H), 2.33 (s, 3H), 1.81 (bd, J ) 13.0 Hz, 2H), 1.61 (qd, J )
6
13
1
1
3.0, 4.4 Hz, 2H), 1.49 (s, 3H); C δ 154.8, 142.8, 135.7, 129.1,
25
26.5, 79.3, 44.4, 42.2, 33.2, 28.4, 20.9. Anal. Calcd for C17H -
NO2: C, 74.14; H, 9.15; N, 5.09. Found: C, 74.03; H, 9.24; N,
.08.
ter t-Bu tyl 4-(4-for m ylp h en yl)p ip er id in e-1-ca r boxyla te
(
2
1
m, 2H), 7.25 (m, 2H), 4.35 (q, J ) 6.80 Hz, 2H), 4.25 (br m,
5
H), 2.79 (t, J ) 12.4 Hz, 2H), 2.69 (tt, J ) 12.4, 3.6 Hz, 1H),
.81 (d, J ) 12.8 Hz, 2H), 1.62 (qd, J ) 12.8, 4.0 Hz, 2H), 1.47
1
(
15): white solid; mp 70-72 °C; 99% assay yield; H NMR (400
1
3
(
s, 9H), 1.37 (t, J ) 6.8 Hz, 3H); C: 166.3, 154.7, 150.8, 129.7,
MHz, CDCl ) δ 9.97 (s, 1H), 7.82 (m, 2H), 7.36 (m, 2H), 4.26 (br
3
1
28.6, 126.7, 79,4m 60.7, 44.1, 42.7, 32.8, 28.4, 14.2. Anal. Calcd
for C19 : C, 68.44; H, 8.16; N, 4.20. Found: C, 68.35; H,
.30; N, 4.20.
ter t-Bu tyl 4-(4-m eth oxyp h en yl)p ip er id in e-1-ca r boxyla te
m, 2H), 2.76 (m, 3H), 1.83 (d, J ) 12.6, 2H), 1.64 (qd, J ) 12.6,
H
27NO
4
4
7
.4, 2H), 1.48 (s, 9H); 13C 191.7, 154.7, 152.8, 134.9, 130.0, 127.4,
9.5, 44.4, 41.7, 33.3, 28.4. Anal. Calcd for C17 : C, 70.56;
8
H
23NO
3
H, 8.01; N, 4.84. Found: C, 70.41; H, 8.06; N, 4.78.
1
(
9): white solid; mp 36-38 °C; 38% assay yield; NMR H δ 7.13
ter t-Bu tyl 4-(4-n itr oph en yl)piper idin e-1-car boxylate (16):
(m, 2H), 6.86 (m, 2H), 4.23 (br m, 2H), 3.79 (s, 3H), 2.79 (t, J )
1
white solid; mp 69-70 °C; 88% assay yield; NMR H 8.18 (m,
1
2.4 Hz, 2H), 2.60 (tt, J ) 12.4, 3.6 Hz), 1H), 1.80 (d, J ) 13.0
13
2H), 7.37 (m, 2H), 4.29 (br m, 2H), 2.81 (m, 3H), 1.85 (d, J )
Hz, 2H), 1.58 (qd, J ) 13.0, 3.6 Hz, 2H), 1.49 (s, 9H); C 158.0,
54.8, 137.9, 127.5, 113.8, 79.3, 55.1, 44.4, 41.7, 33.3, 28.4. Anal.
Calcd for C17 C, 70.07; H, 8.65; N, 4.81; O, 16.47.
1
3
1
1
3.0 Hz, 2H), 1.64 (qd, J ) 4.4, 13.0 Hz, 2H), 1.49 (s, 9H);
C
1
54.6, 153.2, 146.5, 127.6, 123.7, 79.6, 44.0, 42.6, 32.7, 28.4. Anal.
: C, 62.73; H, 7.24; N, 9.14. Found: C,
2.70; H, 7.04; N, 9.04.
ter t-Bu tyl 4-(2-a cetyl-4-ch lor op h en yl)p ip er id in e-1-ca r -
H
3
25NO :
Calcd for C16
22 2 4
H N O
Found: C, 70.09; H, 8.73; N, 4.81.
ter t-Bu tyl 4-[4-m eth oxy-2-(m eth oxyca r bon yl)p h en yl]p i-
p er id in e-1-ca r boxyla te (10): colorless oil; 81% assay yield;
6
1
NMR H δ 7.30 (d, J ) 2.8, 1H), 7.24 (d, J ) 8.8 Hz, 1H), 7.00
boxyla te (17): white solid; mp 80-81 °C; 63% assay yield; NMR
1
(
3
1
dd, J ) 8.8, 2.8 Hz, 1H), 4.22 (br d, J ) 13.2 Hz, 2H), 3.89 (s,
H δ 7.52 (d, J ) 2.40 Hz, 1H), 7.40 (dd, J ) 8.4, 2.4 Hz, 1H),
H), 3.80 (s, 3H), 3.44 (tt, J ) 12.0, 3.2 Hz, 1H), 2.81 (m, 2H),
.79 (d, J ) 10.8 Hz, 2H), 1.57 (qd, J ) 12.4, 2.0 Hz, 2H), 1.48
7.29 (d, J ) 8.4 Hz, 1H), 4.22 (br d, J ) 13.2 Hz), 3.22 (tt, J )
12.0, 3.6 Hz), 2.79 (m, 2H), 2.58 (s, 3H), 1.77 (d, J ) 13.2 Hz,
1
3
13
(s, 9H); C 168.1, 157.2, 154.8, 138.8, 130.4, 127.8, 118.1, 114.8,
2H), 1.56 (qd, J ) 12.4, 4.4 Hz, 2H), 1.48 (s, 9H); C 201.4, 154.7,
7
9.2, 55.3, 52.0, 44.5, 37.7, 33.2, 28.4. Anal. Calcd for C19
NO : C, 65.31; H, 7.79; N, 4.01. Found: C, 65.32; H, 7.88; N,
.06.
ter t-Bu tyl 4-[2-(m eth oxyca r bon yl)-4-n itr op h en yl]p ip er i-
H
27
-
143.3, 139.8, 131.6, 131.2, 128.7, 128.1, 79.4, 44.2, 37.7, 33.1,
30.3, 28.4. Anal. Calcd for C18
4.15. Found: C, 64.17; H, 7.01; N, 4.02.
ter t-Bu tyl 4-p yr id in -2-ylp ip er id in e-1-ca r boxyla te (18):
colorless oil; 63% assay yield; NMR H 8.52 (m, 1H), 7,61 (m,
1H), 7.11 (m, 2H), 4.24 (br m, 2H), 2.83 (m, 3H), 1.90 (d, J )
3
H24ClNO : C, 63.99; H, 7.16; N,
5
4
d in e-1-ca r boxyla te (11): white solid; mp 90-91.5 °C; 60%
1
assay yield; NMR 1H δ 8.68 (d, J ) 2.8 Hz, 1H), 8.30 (dd, J )
8
.8, 2.4 Hz, 1H), 7.54 (d, J ) 8.8 Hz, 1H), 4.27 (br d, J ) 12.8
13.0 Hz, 2H), 1.70 (qd, J ) 13.0, 4.4 Hz, 2H), 1.46 (s, 9H); 13
C
Hz, 2H), 3.97 (s, 9H), 3.69 (tt, J ) 12.0, 3.2 Hz, 1H), 2.85 (m,
164.3, 154.7, 149.2, 136.4, 121.4, 120.8, 79.3, 44.5, 44.0, 31.6,
28.4. Anal. Calcd for C15H22N O : C, 68.67; H, 8.45; N, 10.68.
2
1
1
H), 1.84 (bd, J ) 13.2 Hz, 2H), 1.63 (qd, J ) 8.4, 4.0 Hz, 2H),
2
2
13
.48 (s, 9H); C 166.1, 154.6, 154.2, 145.8, 130.7, 128.2, 126.3,
25.6, 79.6, 52.6, 44.1, 38.6, 32.7, 28.4. Anal. Calcd for
Found: C, 68.59; H, 8.55; N, 10.70.
ter t-Bu tyl 4-[2-(m eth oxyca r bon yl)p h en yl]p ip er id in e-1-
C
18
H
24
N
2
O
6
: C, 59.33; H, 6.64; N, 7.69. Found: C, 59.41; H, 6.48;
1
ca r boxyla te (19): colorless oil; 92% assay yield; NMR H δ 7.80
N, 7.63.
(
dd, J ) 7.6, 1.6 Hz, 1H); 7.47 (td, J ) 7.6, 1.6 Hz, 1H), 7.35 (dd,
ter t-Bu t yl 4-(3-a cet ylp h en yl)p ip er id in e-1-ca r b oxyla t e
J ) 8.0, 1.2 Hz, 1H), 7.26 (td, J ) 7.6, 1.2 Hz, 1 H), 4.25 (br d,
(
12): white solid; mp 67-69 °C; 95% assay yield (80% isolated
J ) 13.2 Hz, 1H), 3.91 (s, 3H), 3.55 (tt, J ) 12.0, 3.6 Hz, 2H),
1
by silica gel chromatography); NMR H δ 7.77-7.83 (m, 2H),
7
2
1
1
3
.84 (td, J ) 13.2, 2.4 Hz, 2H), 1.83 (br d, J ) 13.2 Hz, 2H),
.40-7.43 (m, 2H), 4.27 (d, J ) 12.8 Hz, 2H), 2.81 (m, 2H), 2.72
13
.64 (q of d, J ) 12.4, 4.4 Hz, 2H), 1.49 (s, 9H); C 168.3, 154.8,
(tt, J ) 12.4, 3.6 Hz), 2.60 (s, 3H), 1.84 (d, J ) 13.2 Hz, 2H),
46.7, 131.9, 130.2, 129.6, 126.7, 125.8, 79.3, 51.9, 44.5, 38.3,
1
1
2
.65 (qd, J ) 12.4, 4.4 Hz, 2H), 1.49 (s, 9H); 13C 198.1, 154.7,
46.2, 137.3, 131.5, 128.7, 126.5, 126.4, 79.4, 44.2, 42.5, 33.0,
8.4, 26.6. Anal. Calcd for C18H25NO : C, 71.26; H, 8.31; N, 4.62.
3
4
3.0, 28.4. Anal. Calcd for C18H25NO : C, 67.69; H, 7.89; N, 4.39.
Found: C, 67.64; H, 7.97; N, 4.38.
Found: C, 71.32; H, 8.30; N, 4.62.
J O049647I
J . Org. Chem, Vol. 69, No. 15, 2004 5123