682 J . Org. Chem., Vol. 67, No. 3, 2002
Salvatore et al.
1
127.15, 128.33, 128.41, 139.30. Anal. Calcd for C26H39N: C,
83.41; H, 10.75; N, 3.83. Found: C, 83.29; H, 10.39; N, 3.60.
Dia lk yla m in e 5 (R ) cyclohexylmethyl, R′ ) (CH2)3Ph):
90% yield; IR (film) 3320, 3084, 3062, 3025, 2850, 2807,1495,
1457, 1128, 745 cm-1; 1H NMR (CDCl3) δ 0.80-0.90 (m, 2 H),
1.18-1.26 (m, 4 H), 1.39-1.51 (m, 1 H), 1.68-1.82 (m, 6 H),
2.40 (d, J ) 6.8 Hz, 2 H), 2.58-2.65 (m, 4 H), 7.10-7.28 (m, 5
H); 13C NMR (CDCl3) δ 24.67, 24.82, 29.72, 29.87, 31.68, 36.10,
47.82, 123.84, 126.32, 126.47, 140.32.
Dia lk yla m in e 36: 45% yield; H NMR (CDCl3) δ 2.10 (s,
NH), 2.34-2.64 (m, 8 H), 2.92-3.10 (m, 1 H), 3.39 (AB, J AB
)
13.4 Hz, 2 H), 3.73 (AB, J AB ) 13.4 Hz, 2 H), 7.05-7.30 (m, 20
H); 13C NMR (CDCl3) δ 34.23, 38.44, 49.66, 51.29, 53.63, 59.46,
124.35, 125.00, 126.99, 128.38, 128.77, 129.05, 139.50.
Dia lk yla m in e 5 (R ) 2-methoxyethyl, R′ )(CH2)3Ph): 84%
yield; 1H NMR (CDCl3) δ 1.84-1.90 (m, 2 H), 2.63-2.70 (m, 4
H), 2.80 (t, J ) 5.1 Hz, 2 H), 3.12 (s, NH), 3.34 (s, 3 H), 3.50
(t, J ) 5.0 Hz, 2 H), 7.12-7.33 (m, 5 H); 13C NMR (90 MHz,
CDCl3) δ 30.93, 33.30, 48.79, 48.99, 58.63, 71.17, 125.68,
128.21, 141.66.
Tr ia lk yla m in e 21 (R ) 2-methoxyethyl, R′ ) (CH2)3Ph):
15% yield; IR (film) 3084,3062, 2939, 2861, 2811, 1496, 1453,
1117, 1079, 746 cm-1; 1H NMR (CDCl3) δ 1.77-1.85 (m, 4 H),
2.53-2.57 (m, 4 H), 2.63-2.70 (m, 6 H), 3.33 (s, 3 H), 3.40 (t,
J ) 6.2 Hz, 2 H), 7.17-7.37 (m, 10 H); 13C NMR (CDCl3) δ
28.65, 33.57, 53.34, 54.07, 58.67, 71.12, 125.70, 128.17, 128.28,
142.25.
Dia lk yla m in e 5 (R ) valine, R′ ) Bn): 74% yield; IR (film)
3348, 3104, 3072, 3032, 2960, 2868, 1472, 1038, 709 cm-1; 1H
NMR (CDCl3) δ 0.90 (d, J ) 6.8 Hz, 3 H), 0.94 (d, J ) 6.8 Hz,
3 H), 1.84-1.89 (m, 1 H), 2.44-2.45 (m, 3 H), 3.37 (dd, J )
17.0, 7.2 Hz, 1 H), 3.62 (dd, J ) 17.0, 7.2 Hz, 1 H), 3.72-3.81
(m, 2 H), 7.09-7.31 (m, 5 H); 13C NMR (90 MHz, CDCl3) δ
18.39, 19.55, 28.79, 51.32, 60.35, 63.82, 127.10, 128.12, 128.46.
Dia lk yla m in e 5 (R ) isoleucine, R′ ) Ile-NBn2): 52% yield;
1H NMR (CDCl3) δ 0.86-0.93 (m, 12 H), 1.17-1.19 (m, 2 H),
1.41 (m, 1 H), 1.51-1.54 (m, 2 H), 2.15 (s, 2 H), 2.40-2.47 (m,
2 H), 2.70-2.76 (m, 2 H), 3.30 (m, 1 H), 3.44 (AB, J AB ) 13.5
Hz, 2 H), 3.50-3.53 (m, 1 H), 3.73 (AB, J AB ) 13.5 Hz, 2 H),
7.23-7.37 (m, 10 H); 13C NMR (CDCl3) δ 11.48, 15.92, 16.32,
26.78, 32.77, 46.00, 54.02, 54.48, 58.32, 59.17, 62.84, 127.09,
128.14, 128.95, 139.7.
Tr ia lk yla m in e 21 (R ) cyclohexylmethyl, R′ ) (CH2)3Ph):
1
10% yield; H NMR (CDCl3) δ 0.85-0.87 (m, 2 H), 1.23 (m, 4
H), 1.40-1.45 (m, 1 H), 1.73-1.83 (m, 8 H), 2.18 (d, J ) 3.8
Hz, 2 H), 2.44 (s, 4 H), 2.65 (s, 4 H), 7.18-7.30 (m, 10 H); 13
C
NMR (CDCl3) δ 26.10, 26.80, 28.88, 31.87, 32.79, 33.57, 36.07,
54.10, 61.61, 125.48, 128.26, 128.37, 142.42.
Dia lk yla m in e 5 (R ) cyclopropyl, R′ ) (CH2)3Ph): 83%
yield; 1H NMR (CDCl3) δ 0.56-0.64 (m, 4 H), 2.03-2.05 (m, 2
H), 2.26-2.31 (m, 1 H), 2.73 (t, J ) 7.7 Hz, 2 H), 2.88 (t, J )
7.2 Hz, 2 H) 4.35 (s, NH), 7.25-7.38 (m, 5 H); 13C NMR (CDCl3)
δ 4.17, 28.11, 30.29, 32.89, 48.37, 126.03, 128.20, 128.35,
140.31.
Tr ia lk yla m in e 21 (R ) cyclopropyl, R′ ) (CH2)3Ph): 12%
yield; 1H NMR (CDCl3) δ 0.56-0.59 (m, 4 H), 1.80-1.86 (m, 1
H), 1.96 (d, J ) 2.3 Hz, 4 H), 2.70-2.78 (m, 8 H), 7.09-7.53
(m, 10 H); 13C NMR (CDCl3) δ 6.75, 28.51, 33.83, 36.53, 54.89,
125.55, 128.16, 128.25, 142.37.
Dia lk yla m in e 5 (R ) cyclooctyl, R )(CH2)3Ph): 75% yield;
1H NMR (CDCl3) δ 1.27-1.86 (m, 17 H), 2.61-2.65 (m, 5 H),
7.17-7.39 (m, 5 H); 13C NMR (CDCl3) δ 24.00, 25.61, 27.10,
31.78, 32.52, 33.63, 46.86, 57.78, 125.55, 128.12, 128.17,
141.96.
Tr ia lk yla m in e 21 (R ) cyclooctyl, R′ ) (CH2)3Ph): 10%
1
yield; H NMR (CDCl3) δ 1.26-1.89 (m, 22 H), 2.54-2.64 (m,
5 H), 7.21-7.33 (m, 10 H); 13C NMR (CDCl3) δ 23.95, 25.57,
27.06, 31.73, 32.48, 33.59, 46.81, 57.74, 125.50, 128.07, 128.13,
141.92.
Dia lk yla m in e 5 (R ) valine methyl ester, R′ ) 5-pentenyl):
65% yield; [R]25 ) -10.0 (lit.25 [R]25 ) -9.9 (c ) 1.8 in
D
D
CHCl3)); IR (film) 3355, 3085, 2973, 2933, 1742, 1643, 1472,
1183, 992, 775 cm-1; 1H NMR (CDCl3) δ 0.95 (d, J ) 6.8 Hz, 3
H), 0.96 (d, J ) 6.8 Hz, 3 H), 1.5-1.64 (m, 2 H), 1.62 (s, 1 H),
1.93 (m, 1 H), 2.13 (m, 2 H), 2.41 (m, 1 H), 2.61 (m, 1 H), 2.95
(d, J ) 6.1, 1 H), 3.70 (s, 3 H), 4.95 (dd, J ) 10.2, 1.3 Hz, 1 H),
5.01 (m, 1 H), 5.80 (m, 1 H); 13C NMR (CDCl3) δ 18.81, 19.15,
29.33, 31.38, 31.65, 48.12, 51.35, 67.48, 114.30, 138.50, 175.90.
Dia lk yla m in e 5 (R ) valine methyl ester, R′ ) allyl): 60%
Dia lk yla m in e 5 (R ) adamantyl, R′ ) (CH2)3Ph): 82%
yield; IR (film) 3350, 3061, 3024, 2910, 2847, 2769, 1497, 1451,
1197, 750 cm-1; 1H NMR (CDCl3) δ 1.57-1.72 (m, 15 H), 1.81-
1.90 (m, 2 H), 2.10 (s, NH), 2.62-2.68 (m, 4 H), 7.16-7.30 (m,
5 H); 13C NMR (CDCl3) δ 29.29, 29.58, 32.14, 33.83, 36.67,
39.86, 41.99, 42.28, 51.48, 125.83, 128.29, 128.44, 141.86.
Dia lk yla m in e 5 (R ) adamantyl, R′ ) cinnamyl): 66%
yield; IR (film) 3310, 3050, 3024, 3000, 2910, 2847, 1650, 1448,
1
yield; H NMR (CDCl3) δ 0.90 (d, J ) 6.8 Hz, 3 H), 0.91 (d, J
1
968, 691 cm-1; H NMR (CDCl3) δ 1.58-1.75 (m, 15 H), 2.50
) 6.8 Hz, 3 H), 1.55 (m, NH), 1.83 (m, 1H), 3.02-3.06 (m, 2
H), 3.26 (m, 1 H), 3.65 (s, 3 H), 4.97 (m, 1 H), 5.12 (m, 1 H),
5.80 (ddt, J ) 17.0, 10.4, 6.0 Hz, 1 H); 13C NMR (CDCl3) δ
18.35, 19.21, 31.34, 50.21, 51.03, 66.05, 115.84, 136.31, 156.03,
175.38.
(s, NH), 3.44 (d, J ) 7.9 Hz, 2 H), 6.35 (dt, J ) 16.8, 7.4 Hz,
1 H), 6.53 (d, J ) 16.8 Hz, 1 H), 7.19-7.39 (m, 5 H); 13C NMR
(CDCl3) δ 29.42, 36.47, 42.16, 42.88, 51.46, 126.19, 127.21,
128.38, 131.36, 136.99.
Dia lk yla m in e 5 (R ) t-Bu, R′ ) (CH2)3Ph): 90% yield; IR
Dia lk yla m in e 5 (R ) valine methyl ester, R′ ) Bn): 60%
(film) 3300, 3062, 3026, 2933, 2859, 2824, 2815, 1496, 1453,
yield; [R]25 ) -49.5 (lit.25 [R]25 ) -50.2 (c ) 1.0 in MeOH));
D
D
1232, 744 cm-1; H NMR (CDCl3) δ 1.08 (s, 9 H), 1.78-1.83
1H NMR (CDCl3) δ 0.94 (d, J ) 6.8 Hz, 6 H), 1.77 (s, NH),
1
(m, 2 H), 2.05 (s, NH), 2.56-2.64 (m, 4 H), 7.14-7.25 (m, 5
H); 13C NMR (CDCl3) δ 28.73, 32.26, 33.63, 41.88, 50.31,
125.53, 128.09, 128.17, 141.92. Anal. Calcd for C13H21N: C,
76.61; H, 10.06; N, 6.32. Found: C, 75.36; H, 10.13; N, 6.38.
Dia lk yla m in e 5 (R ) tert-octyl, R′ ) Bn): 87% yield; 1H
NMR (CDCl3) δ 1.00 (s, 9 H), 1.17 (s, 6 H), 1.45 (s, 2 H), 3.68
(s, 2 H), 7.04-7.30 (m, 5 H); 13C NMR (CDCl3) δ 29.04, 31.72,
46.57, 53.01, 54.44, 126.53, 128.07, 128.24, 141.57. Anal. Calcd
for C15H25N: C, 81.75; H, 11.49; N, 6.35. Found: C, 81.94; H,
11.44; N, 6.26.
1.89-1.94 (m, 1 H), 3.01 (d, J ) 6.1 Hz, 1 H), 3.58 (AB, J AB )
12.5 Hz, 1 H), 3.71 (s, 3 H), 3.82 (AB, J AB ) 12.5 Hz, 1 H),
7.23-7.7.3 (m, 5 H). 13C NMR (CDCl3) δ 18.54, 19.20, 31.59,
51.26, 52.43, 66.44, 126.86, 128.13, 128.16, 139.97, 175.65.
Anal. Calcd for C13H19NO2: C, 70.56; H, 8.65; N, 6.33. Found:
C, 70.23; H, 8.70; N, 6.35.
Dim er 42: 52% yield; 1H NMR (CDCl3) δ 0.74-0.86 (m, 12
H), 1.22-1.52 (m, 5 H), 1.73-1.85 (m, 2 H), 2.87-2.93 (m, 2
H), 3.34 (m, 1 H), 3.71-3.73 (m, 1 H), 3.80-3.83 (m, 1 H), 6.88
(br s, 4 H).
1
1
Dia lk yla m in e 5 (R ) octyl, R′ ) Bu): 93% yield; H NMR
Tr im er 44: 46% yield; H NMR (CDCl3) δ 0.70-0.93 (m,
(CDCl3) δ 0.86-0.91(m, 6 H), 1.25 (m, 12 H), 1.39 (m, 4 H),
2.35-2.39 (m, 4 H); 13C NMR (CDCl3) δ 14.06, 20.77, 22.63,
26.96, 27.63, 29.14, 29.29, 29.57, 31.83, 53.90, 54.21. Anal.
Calcd for C12H27N: C, 78.76; H, 14.68; N, 5.56. Found: C,
79.46; H, 14.45; N, 5.72.
12 H), 1.07 (s, 6 H), 1.29-1.42 (m, 8 H), 2.45-2.51 (m, 1 H),
2.73-2.76 (m, 1 H), 3.19 (s, 3 H), 3.39-3.47 (m, 6 H), 3.86
(AB, J ) 13.5 Hz, 2 H), 4.00 (AB, J ) 13.4 Hz, 2 H), 7.08-
7.38 (m, 10 H).
Dia m in e 48 (R ) 1,2-diaminopropane, R′ ) (CH2)3Ph): 77%
yield; 1H NMR (D2O) δ 0.96 (m, 3 H), 1.68 (m, 2 H), 2.36-2.45
(m, 6 H), 3.00 (m, 1 H), 7.06-7.17 (m, 5 H); 13C NMR (D2O)
21.49, 32.45, 35.36, 48.05, 50.77, 56.44, 128.28, 130.87, 144.58.
Dia m in e 48 (R ) L-lysine methyl ester, R′ ) Bn): 70% yield;
1H NMR (CHCl3) δ 1.49 (m, 2 H), 1.56 (m, 2 H), 1.58 (m, 2 H),
2.42 (m, 2 H), 3.55 (m, 1 H), 3.60 (s, 2 H), 3.80 (s, 3 H), 7.24-
7.39 (m, 5 H); 13C NMR (CHCl3) 23.43, 26.74, 34.78, 51.84,
Dia lk yla m in e 34: 54% yield; 1H NMR (CDCl3) δ 0.87-
0.92 (m, 6 H), 1.17-1.21 (m, 1 H), 1.43-1.47 (m, 1 H), 1.88
(m, 1 H), 2.57 (d, J ) 8.5 Hz, 2 H), 2.66-2.79 (m, 5 H), 2.8 (s,
NH), 2.97-3.46 (AB, J AB ) 13.4 Hz, 2 H), 3.74-3.78 (AB, J AB
) 13.7 Hz, 2 H), 7.12-7.41 (m, 15 H); 13C NMR (CDCl3) δ
12.13, 16.43, 29.07, 32.52, 36.48, 47.31, 51.25, 54.36, 60.95,
126.41, 127.03, 128.42, 128.63, 129.09, 140.25, 140.40.