7320 J . Org. Chem., Vol. 65, No. 22, 2000
Guillena and Na´jera
(2S,4′S,5′R)-2-Am in o-1-(3′,4′-d im eth yl-2′-oxo-5′-p h en yl-
1′-im id a zolyd in yl)-4-m eth yl-4-p en ten -1-on e [(-)-27k , d e
98%]: Rf 0.43 (MeOH); [R]25D -73.09° (c 4.6, CHCl3); IR 3688-
3179, 1736, 1678; 1H NMR δ 0.79 (d, J ) 6.7, 3H), 1.80 (s,
3H), 1.72 (br s, 2H, NH2), 1.87, 2.62 (2dd, 2H, J ) 3.0, 10.0,
12.8), 2.82 (s, 3H), 3.91 (dq, J ) 6.7, 8.6, 1H), 4.70, 4.83 (2s,
2H), 4.87 (dd, J ) 3.7, 9.8, 1H), 5.22*, 5.31 (d, J ) 8.6, 1H),
7.12, 7.29 (m, 5H); 13C NMR δ 14.9*, 15.0, 21.7, 22.1*, 28.1*,
28.2, 43.3*, 43.9, 51.3, 51.5*, 54.0*, 54.1, 59.3, 59.5*, 113.3*,
113.9, 126.9, 128.0*, 128.2, 128.25*, 128.3*, 128.5, 132.4*,
136.5, 142.0, 155.3, 175.2*, 175.3; MS m/e 301 (M+, 7), 84 (100);
HRMS calcd for C17H23N3O2: 301.1815. Found 301.1790.
(2S,4′S,5′R)-2-Am in o-1-(3′,4′-d im eth yl-2′-oxo-5′-p h en yl-
1′-im id a zolyd in yl)-5-m eth yl-4-h exen -1-on e [(-)-27l, d e
98%]: Rf 0.42 (MeOH); [R]25D -50.09° (c 3.3, CHCl3); IR 3703-
3.92 (dq, J ) 6.7, 8.6, 1H), 4.56*, 5.63 (2dd, J ) 4.3, 8.5, 1H),
5.25*, 5.29 (2d, J ) 8.5, 1H), 7.11, 7.31 (2m, 5H); 13C NMR δ
15.1, 28.1*, 28.2, 29.2*, 29.6*, 30.2, 30.7, 51.5, 52.8*, 53.0, 54.1,
59.2, 126.9, 128.2, 128.4*, 128.6, 128.7*, 132.4*, 136.4, 155.3,
168.9, 175.6; MS m/e 333 (M+, (<1), 58 (100); HRMS calcd for
C
17H23N3O4: 333.1689. Found 333.1664.
ter t-Bu tyl (4S,4′S,5′R)-4-a m in o-5-(3′,4′-d im eth yl-2′-oxo-
5′-p h en yl-1′-im id a zolyd in yl)-5-oxop en ta n oa te [(-)-27r ,
d e 94%]: Rf 0.78 (MeOH); [R]25 -25.81° (c 2.4, CHCl3); IR
D
3749-3110, 1724, 1678, 1642; 1H NMR δ 0.79 (d, J ) 6.7, 3H),
1.38*, 1.41 (2s, 9H), 1.80 (br s, 2H, NH2), 1.68, 2.03 (2m, 4H),
2.27 (m, 2H), 2.76*, 2.85 (2s, 3H), 3.91 (dq, J ) 6.7, 8.6, 1H),
4.66 (dd, J ) 4.0, 8.5, 1H), 5.19*, 5.31 (2d, J ) 8.7, 1H), 7.14,
7.30 (2m, 5H); 13C NMR δ 15.1, 28.2, 29.1, 30.3, 32.0, 53.0,
54.1, 59.2, 80.5, 126.9, 128.2, 128.6, 136.5, 155.3, 172.7, 175.6;
MS m/e (DIP) 375 (M+, <1), 102 (100); HRMS calcd for
1
3112, 1735, 1686; H NMR δ 0.78 (d, J ) 6.7, 3H), 1.54, 1.63
(2s, 6H), 1.74 (br s, 2H, NH2), 2.14, 2.46 (2m, 2H), 2.80 (s, 3H),
3.89 (dq, J ) 6.7, 8.6, 1H), 4.71 (m, 1H), 5.00 (t, J ) 7.3, 1H),
5.27 (d, J ) 8.6, 1H), 7.12, 7.31 (m, 5H); 13C NMR δ 15.1, 17.9,
26.9, 28.2, 53.5, 54.1, 59.2, 119.7, 127.0, 128.1, 128.5, 134.9,
136.5, 155.4, 175.6; MS m/e 315 (M+,<1), 246 (100); HRMS
calcd for C18H25N3O2: 315.1976. Found 315.1947.
C
20H29N3O4: 375.2158. Found 375.2110.
Eth yl (3Z,4′S,5′R)-5-(3′,4′-d im eth yl-2′-oxo-5′-p h en yl-1′-
im idazolydin yl)-4-diph en ylm eth ylen eam in o-5-oxo-3-pen -
ten oa te [(-)-28]: Rf 0.39 (hexane/EtOAc: 1/1); IR 1737, 1693,
1
1667, 1574; H NMR δ 0.68 (d, J ) 6.3, 3H) 1.23 (t, J ) 7.0,
3H), 1.73 (br s, 2H, NH2), 2.78 (2s, 3H), 3.38, 3.49 (2dd, J )
7.3, 17.1, 6.7, 17.1, 2H), 3.53 (dq, J ) 6.7, 8.5, 1H), 4.11 (q, J
) 7.1, 2H), 4.74 (d, J ) 8.5, 1H), 5.07 (t, J ) 16.7, 1H), 7.00,
7.32, 7.69 (3m, 15H); 13C NMR δ 14.2, 15.1, 28.3, 32.9, 53.7,
59.4, 60.7, 70.0, 121.5, 126.9, 127.7, 127.9, 128.0, 128.4, 129.0,
129.5, 129.6, 130.6, 136.1, 137.3, 139.5, 154.0, 168.1, 171.1,
171.2; MS m/e (DIP) 511 (M+ + 2, 1), 510 (M+ + 1, 4), 509
(M+, 9), 165 (100); HRMS calcd for C30H29N3O4: 509.2315.
Found 509.2367.
(2S,4E,4′S,5′R)-2-Am in o-1-(3′,4′-dim eth yl-2′-oxo-5′-ph en -
yl-1′-im id a zolyd in yl)-5-p h en yl-4-p en ten -1-on e [(-)-27m ,
d e 98%]: Rf 0.35 (MeOH); [R]25 -43.28° (c 3.2, CHCl3); IR
D
3672-3156, 1732, 1682; 1H NMR δ 0.80 (d, J ) 6.7, 3H), 1.79
(br s, 2H, NH2), 2.39, 2.74 (2m, 2H), 2.83 (s, 3H), 3.92 (dq, J )
6.7, 8.5, 1H), 4.89 (m, 1H), 5.34 (d, J ) 8.5, 1H), 6.05 (dt, J )
7.3, 15.9, 1H), 6.36 (d, J ) 15.9, 1H), 7.26 (m, 10H); 13C NMR
δ 15.1, 28.3, 39.1, 53.1, 54.1, 59.3, 125.5, 126.2, 127.1, 128.1,
128.4, 128.5, 130.1, 133.2, 136.5, 137.2, 155.4, 175.1; MS m/e
(2S,4′S,5′R)-2-Am in o-3-(d im eth yla m in o)-1-(3′,4′-d im e-
th yl-2′-oxo-5′-ph en yl-1′-im idazolydin yl]pr opan -1-on e [(-)-
(DIP) 348 (M+ - 17, 1), 246 (100); HRMS calcd for C22H25
N3O2: 363.1947. Found 363.1948.
-
1
29, d e 74%]: Rf 0.46 (MeOH); IR 3710-3100, 1726, 1650; H
(2S,4′S,5′R)-2-Am in o-3-(1,3-b en zod ioxol-5-yl)-1-(3′,4′-
d im et h yl-2′-oxo-5′-p h en yl-1′-im id a zolyd in yl)p r op a n -1-
on e [(-)-27n , d e 84%]: Rf 0.34 (MeOH); IR 3673-3181, 1727,
NMR δ 0.73*, 0.76 (d, J ) 6.7, 3H), 1.78 (br s, 2H, NH2), 2.26,
2.28* (s, 6H), 2.52 (dd, J ) 4.0, 14.6, 1H), 2.76 (m with 2s at
2.74 and 2.81, 4H), 3.92 (dq, J ) 6.7, 8.5, 1H), 4.87 (dd, J )
4.0, 9.8, 1H), 5.25*, 5.31 (d, J ) 8.6, 1H), 7.13, 7.28 (m, 5H);
13C NMR δ 14.9*, 15.0, 28.1*, 28.2, 45.6, 45.8*, 51.5*, 51.8,
54.0*, 54.1, 59.2, 59.6*, 63.0*, 63.6, 128.1*, 128.3, 128.5,
128.55*, 128.6 130.0, 136.4, 155.3, 174.2; MS m/e (DIP) 304
(M+, <1%), 58 (100); HRMS calcd for C16H24N4O2: 304.1899.
Found 304.1854.
1
1681; H NMR δ 0.74*, 0.80 (d, J ) 6.7, 3H), 1.75 (br s, 2H,
NH2), 2.30, 2.46*, 2.99*, 3.17 (2dd, J ) 3.7, 9.1, 13.4, 2H),
2.82*, 2.84 (s, 3H), 3.93 (dq, J ) 6.7, 8.6, 1H), 4.87 (m, 1H),
5.26*, 5.32 (d, J ) 8.6, 1H), 5.90 (s, 2H), 6.64, 6.67, 7.12, 7.29
(4m, 8H); 13C NMR δ 15.0, 28.1*, 28.2, 41.4, 54.1, 55.1, 59.2,
100.8, 108.8, 109.9, 122.6, 127.0, 128.2, 128.6, 131.7, 136.5,
146.2, 147.6, 155.4, 174.8; MS m/e (DIP) 381 (M+, 5), 369 (M+
- 12, 10), 44 (100); HRMS calcd for C20H25N3O4: 369.1689.
Found 369.1658.
(3′S,4R,5S)-1,5-Dim eth yl-4-p h en yl-3-(1′,2′,3′,4′-tetr a h y-
d r o-3′-isoqu in olin ylca r bon yl]-2-im id a zolid in on e [(-)-30,
d e 88%]: Rf 0.55 (MeOH); [R]25 -58.24° (c 1.05, CHCl3); tR
D
(2S,4′S,5′R)-2-Am in o-1-(3′,4′-d im eth yl-2′-oxo-5′-p h en yl-
1′-im id a zolyd in yl)-3-(2-n a p h th yl)p r op a n -1-on e [(-)-27o,
17.98*, 18.24; IR 3723-3103, 1726, 1681; 1H NMR δ 0.78*,
0.81 (2d, J ) 6.7, 3H), 1.81 (br s, 1H, NH), 2.64, 3.15 (2dd, J
) 10.4, 16.5, 4.3, 16.5, 2H), 2.79*, 2.83 (2s, 3H), 3.93 (dq, J )
6.7, 8.6, 1H), 4.00, 4.01* (2s, 2H), 5.00 (dd, J ) 4.3, 10.4, 1H),
5.30*, 5.36 (2d, J ) 8.6, 1H), 7.09, 7.31 (2m, 9H); 13C NMR δ
15.0, 28.2, 31.4, 32.1*, 46.6*, 47.1, 54.0*, 54.1, 55.2, 57.6*, 59.2,
125.6, 126.0, 126.1, 126.9, 127.0*,127.2*, 128.0*, 128.2, 128.3*,
128.5*, 128.6, 129.2, 133.8, 135.5, 136.5, 155.3, 172.8; MS m/e
(DIP) 349 (M+, <1), 132 (100); HRMS calcd for C21H23N3O2:
349.1790. Found 349.1765.
d e 98%]: Rf 0.34 (MeOH); [R]25 -27.01° (c 1.6, CHCl3); IR
D
3716-3131, 1720, 1678; 1H NMR δ 0.70*, 0.78 (d, J ) 6.7, 3H),
1.73 (br s, 2H, NH2), 2.61, 3.42 (2m, 2H), 2.84, 2.91* (s, 3H),
3.95 (dq, J ) 6.7, 8.6, 1H), 5.16 (m, 1H), 5.36 (d, J ) 8.6, 1H),
7.23, 7.42, 7.57, 7.68, 7.76 (5m, 12H); 13C NMR δ 14.8*, 14.9,
28.0*, 28.3, 29.7, 53.9*, 54.2, 57.7*, 58.1, 59.0*, 59.2, 125.2*,
125.6, 125.7*, 125.8, 126.8*, 127.1*, 127.2, 127.5, 127.6*, 127.8,
127.9, 128.0*, 128.1, 128.15*, 128.3, 128.4*, 128.5, 130.1, 132.4,
133.1*, 133.4, 133.7*, 134.1, 135.5*, 136.3, 155.1*, 155.3, 171.2;
MS m/e (DIP) 388 (M+ + 1, 3), 387 (M+, 11), 248 (100); HRMS
calcd for C24H25N3O2: 387.1947. Found 387.1934.
(2S,4′S,5′R)-[(3′,4′-Dim eth yl-2′-oxo-5′-p h en yl-1′-im id a -
zolydin yl)(1,3,4,6-tetr ah ydr o-2-pyr idin yl)]m eth an on e [(-)-
31, d e 94%]: Rf 0.33 (MeOH); IR 3697-3127, 3054, 3032, 1727,
1686;1H NMR δ 0.77 (d, J ) 6.7, 3H), 1.82 (br s, 1H, NH),
1.93, 2.47 (2m, 2H), 2.80 (s and m, 5H, CH3N), 3.93 (dq, J )
6.7, 8.6, 1H), 4.83 (dd, J ) 4.3, 9.8, 1H), 5.34 (d, J ) 8.6, 1H),
5.68, 5.78 (2m, 2H), 7.11, 7.27 (2m, 5H); 13C NMR δ 15.3, 28.1,
28.4, 44.1, 54.4, 54.5, 59.3, 124.6, 127.0, 127.1, 128.4, 128.8,
136.8, 155.5, 172.9; MS m/e 300 (M+ + 1, 1), 299 (M+, 4), 82
(100); HRMS calcd for C17H21N3O2: 299.1638. Found 299.1639.
(2S,4′S,5′R)-[(3′,4′-Dim eth yl-2′-oxo-5′-p h en yl-1′-im id a -
zolyd in yl)-(5-m eth yl-3,4-d ih yd r o-2H-2-p yr r olyl)]m eth a -
n on e [(-)-32]: Rf 0.51 (MeOH); tR 15.50; IR 1726, 1688, 1677;
1H NMR δ 0.75 (d, J ) 6.7, 3H), 1.93, 2.50 (2m, 4H), 2.09 (s,
3H), 2.79 (s, 3H), 3.91 (dq, J ) 6.7, 8.6, 1H), 5.25 (d, J ) 8.6,
1H), 5.97 (t, J ) 7.3, 1H), 7.12, 7.25 (2m, 5H); 13C NMR δ 14.8,
19.4, 26.4, 28.1, 32.5, 54.0, 59.3, 72.3, 126.9, 128.1, 128.5, 136.5,
155.4, 170.9, 180.9; MS m/e 301 (M+ + 2, (1), 300 (M+ + 1, 2),
299 (M+, 12), 41 (100); HRMS calcd for C17H21N3O2: 299.1638.
Found 299.1639.
(2S,4′S,5′R)-2-Am in o-1-(3′,4′-d im eth yl-2′-oxo-5′-p h en yl-
1′-im id a zolyd in yl)-4-p h en ylbu ta n e-1,4-d ion e [(-)-27p , d e
92%]: Rf 0.19 (MeOH); IR 3722-3144, 1736, 1678; 1H NMR δ
0.77*, 0.80 (2d, J ) 6.7, 3H), 1.80 (br s, 2H, NH2), 2.81*, 2.83
(s, 3H), 3.08, 3.40*, 3.54, 3.73* (4dd, J ) 4.9, 7.3, 17.1, 2H),
3.98 (dq, J ) 6.7, 8.6, 1H), 5.18*, 5.32 (2d, J ) 8.6, 1H), 5.24,
5.41* (dd, J ) 5.5, 7.3, 1H), 7.37, 7.90 (m, 10H); 13C NMR δ
15.1, 15.2*, 28.1*, 28.3, 41.5*, 43.4, 50.4, 54.1*, 54.2, 59.4,
127.0, 127.9*, 128.1, 128.3*, 128.4*, 128.5, 128.55, 128.7*,
132.6*, 133.0, 136.2, 136.8, 137.0*, 155.4, 174.3, 197.5; MS m/e
(DIP) 385 (M+, <2), 77 (100); HRMS calcd for C21H23N3O3:
365.1739. Found 365.1771.
(4S,4′S,5′R)-Meth yl 4-a m in o-5-(3′,4′-d im eth yl-2′-oxo-5′-
p h en yl-1′-im id a zolyd in yl)-5-oxop en ta n oa te [(-)-27q, d e
80%]: Rf 0.56 (MeOH); tR 16.95*, 17.50; IR 3746-3100, 1726,
1692, 1677; 1H NMR δ 0.77 (d, J ) 6.7, 3H), 1.65 (m, 4H),
1.78 (br s, 2H, NH2), 2.79, 2.81* (2s, 3H), 3.62, 3.63* (2s, 3H),