6
Tetrahedron
1H, J = 8.5 Hz, 1(S,S)), 3.48-3.45 (dd, 1H, J = 5.4
4.6.12. (S)-2-Amino-N-(tert-butyl)-3-
ACCEPTED MANUSCRIPT
Hz, J = 1.2 Hz, 1(S,S)+1(S,R)), 2.12-2.10. (m, 1H,
1(S,S)+1(S,R)), 1.051-1.034(d, 3H, 6.8 Hz,
1(S,S)), 1.044-1.027 (d, 3H, J = 6.8 Hz, 1(S,R)),
1.017-1.000 (d, 3H, J = 6.8 Hz, 1(S,S)), 1.012-
0.995 (d, 3H, J = 6.8 Hz, 1(S,R)); 1 3 C NMR (100
phenylpropanamide (2e)2 7
1 H NMR (400 MHz, CDCl3 ): δ 7.35-7.24 (m,
5H), 7.00 (br s, 1H), 3.57-3.53 (dd, 1H, J = 8.7 Hz,
J = 4.7 Hz), 3.25-3.20 (dd, 1H, J = 13.7 Hz, J = 4.7
Hz), 2.81-2.75 (dd, 1H, J = 13.7 Hz, J = 8.7 Hz),
2.02 (br s, 2H), 1.34 (s, 9H); 1 3 C NMR (125 MHz,
CDCl3 ): δ 172.9, 137.9, 129.4, 128.6, 126.7, 56.8,
50.5, 40.8, 28.6.
J
=
MHz, CDCl3 ):
δ 171.0, 170.8, 142.01, 141.97,
128.56, 128.54, 127.40, 127.38, 126.44, 126.40,
74.8, 74.7, 69.13, 69.06, 55.4, 55.3, 32.1, 32.0,
19.3, 17.5, 17.3.
4.6.13. 2-(4-Hydroxybenzyl)benzaldehyde (9a)1 6
1 H NMR (400 MHz, CDCl3 ): δ 10.24 (s, 1H),
7.87-7.85 (dd, 1H, J = 7.6 Hz, 1.4 Hz), 7.55-7.51
(td, 1H, J = 7.5 Hz, 1.5 Hz), 7.43-7.39 (td, 1H, J =
7.5 Hz, 0.9 Hz), 7.28-7.26 (d, 1H, J = 7.4 Hz),
7.00-6.98 (d, 2H, J = 8.7 Hz), 6.75-6.73 (d, 2H, J =
8.6 Hz), 4.36 (s, 2H); 1 3 C NMR (100 MHz, CDCl3 ):
δ 192.9, 154.1, 143.6, 134.1, 133.7, 132.3, 132.0,
131.5, 129.8, 126.9, 115.4, 37.2.
4.6.8. (S)-2-Amino-N-((R or S)-2-hydroxy-1-
2 6
phenylethyl)-3-methylbutanamide (2a)2 5 ,
1 H NMR (400 MHz, CDCl3 ): δ 8.16-8.14 (d, 1H,
J = 7.4 Hz, 2a(S,S)), 8.09-8.08 (d, 1H, J = 7.2 Hz,
2a(S,R)) 7.37-7.28 (m, 5H, 2a(S,S)+2a(S,R)), 5.10-
5.04 (m, 1H, 2a(S,S)+2a(S,R)), 3.87-3.83 (m, 2H,
2a(S,S)+2a(S,R)), 3.41-3.40 (d, 1H, J = 4.6 Hz,
2a(S,S)) , 3.32-3.31 (d, 1H, J = 3.9 Hz, 2a(S,R)),
2.86 (br s, 3H, 2a(S,S)+2a(S,R)), 2.33-2.21 (m, 1H,
2a(S,S)+2a(S,R)), 0.98-0.96 (dd, 6H, J = 6.9 Hz, J
= 1.4 Hz, 2a(S,S)), 0.91-0.90 (d, 3H, J = 6.9 Hz,
2a(S,R)), 0.79-0.78(d, 3H, J = 6.9 Hz, 2a(S,R)); 1 3 C
NMR (100 MHz, CDCl3 ): δ175.1, 174.1, 139.0,
138.8, 128.8, 127.80, 127.77, 126.74, 126.67, 67.0,
66.8, 60.1, 60.0, 56.2, 56.0, 31.0, 30.8, 19.7, 19.4,
16.6, 16.1.
4.6.14. 2-Benzylbenzaldehyde (9b)1 6
1 H NMR (400 MHz, CDCl3 ): δ 10.26 (s, 1H),
7.85-7.87 (dd, 1H, J = 7.6 Hz, 1.4 Hz), 7.55-7.51
(td, 1H, J = 7.5 Hz, 1.5 Hz), 7.44-7.42 (td, 1H, J =
7.6 Hz, 1.0 Hz), 7.30-7.26 (m, 3H), 7.21-7.14 (m,
3H), 4.46 (s, 2H); 1 3 C NMR (100 MHz, CDCl3 ): δ
192.4, 143.0, 140.2, 133.9, 132.0, 131.6, 128.8,
128.6, 127.0, 126.3, 38.0.
4.6.9. (S)-2-Amino-N-(1-hydroxy-2-methylpropan-2-
yl)-3-methylbutanamide (2b)
1 H NMR (400 MHz, CDCl3 ): δ 7.59 (s, 1H),
3.62-3.51 (m, 2H), 3.29-3.28 (d, 1H, J = 4.1 Hz),
2.33-2.25 (m, 1H), 1.29-1.28 (d, 6H, J = 3.2 Hz),
1.00-0.98 (d, 3H, J = 7.0 Hz), 0.85-0.83 (d, 3H, J =
6.9 Hz); 1 3 C NMR (100 MHz, CDCl3 ): δ 174.5,
59.8, 55.8, 30.6, 24.8, 24.6, 19.5, 16.1; ESI-MS(+)
m/z calcd. For C9 H2 1 N2 O2 [M+H]+ : 189.1598, found
[M+H]+ : 189.1598.
4.6.15. 2-(3-Methylbenzyl)benzaldehyde (9c)1 9
1 H NMR (400 MHz, CDCl3 ): δ 10.27 (s, 1H),
7.89-7.86 (dd, 1H, J = 7.6 Hz, 1.5 Hz), 7.55-7.51
(td, 1H, J = 7.5 Hz, 1.5 Hz), 7.44-7.40 (td, 1H, J =
7.4 Hz, 0.9 Hz), 7.28-7.26 (d, 1H, J = 7.7 Hz),
7.19-7.15 (t, 1H, J = 7.6 Hz), 7.03-7.00 (d, 1 H, J =
7.6 Hz), 6.97-6.93 (m, 2H), 4.42 (s, 2H), 2.30 (s,
3H); 1 3 C NMR (100 MHz, CDCl3 ): δ 192.4, 143.1,
140.2, 138.2, 133.9, 131.7, 131.6, 129.5, 128.4,
127.0, 126.9, 125.8, 37.9, 21.4.
4.6.10. (S)-2-Amino-N-(1-hydroxy-2-methylpropan-
2-yl)-3-phenylpropanamide (2c)
1 H NMR (500 MHz, CDCl3 ): δ 7.38 (br s, 1H),
7.33-7.22 (m, 5H), 3.68-3.65 (dd, 1H, J = 8.4 Hz, J
= 4.9 Hz), 3.63-3.61 (d, 1H, J =12 Hz), 3.52-3.50
(d, 1H, J = 12 Hz), 3.20-3.16 (dd, 1H, J =13.7 Hz, J
= 4.9 Hz), 2.85-2.81 (dd, 1H, J = 13.7 Hz, J = 8.4
Hz), 1.25 (s, 3H), 1.21 (s, 3H); 1 3 C NMR (125 MHz,
CDCl3 ): δ 174.2, 137.1, 129.4, 128.7, 127.0, 70.4,
56.1, 55.7, 40.4, 24.8, 24.4; ESI-MS(+) m/z calcd.
For C1 3 H2 1 N2 O2 [M+H]+ : 237.1598, found [M+H]+ :
237.1598.
4.6.16. 2-(4-Methylbenzyl)benzaldehyde (9d)1 6
1 H NMR (400 MHz, CDCl3 ): δ 10.26 (s, 1H),
7.87-7.85 (dd, 1H, J = 7.6 Hz, 1.4 Hz), 7.54-7.50
(td, 1H, J = 7.5 Hz, 1.4 Hz), 7.42-7.38 (td, 1H, J =
7.5 Hz, 0.7 Hz), 7.27-7.25 (d, 1H, J = 7.4 Hz),
7.09-7.07 (d, 2H, J = 7.9 Hz), 7.03-7.02 (d, 2H, J =
8.0 Hz), 4.40 (s, 2H), 2.30 (s, 3H); 1 3 C NMR (100
MHz, CDCl3 ): δ 192.4, 143.4, 137.2, 135.8, 133.9,
131.8, 131.6, 129.3, 128.7, 126.9, 37.6, 21.0.
4.6.17. 2-(2-Methoxybenzyl)benzaldehyde (9e)2 8
1 H NMR (400 MHz, CDCl3 ): δ 10.36 (s, 1H),
7.90-7.87 (dd, 1H, J = 7.7 Hz, 1.4 Hz), 7.49-7.47
(td, 1H, J = 7.5 Hz, 1.6 Hz), 7.39-7.35 (td, 1H, J =
7.5 Hz, 0.6 Hz), 7.24-7.19 (m, 2H), 6.95-6.93 (dd,
1H, J = 7.3 Hz), 6.88-6.84 (m, 2H), 4.40 (s, 2H),
3.81 (s, 3H); 1 3 C NMR (100 MHz, CDCl3 ): δ 192.4,
157.0, 143.3, 134.0, 133.8, 131.3, 130.2, 130.0,
128.7, 127.7, 126.6, 120.6, 110.3, 55.2, 31.8.
4.6.11. (S)-2-Amino-N-(1-hydroxy-2-methylpropan-
2-yl)-4-methylpentanamide (2d)
1 H NMR (400 MHz, CDCl3 ): δ 7.60 (s, 1H),
3.62-3.51 (m, 2H), 3.41-3.37 (m, 1H), 3.11 (br s,
2H), 1.70-1.66 (m, 2H,), 1.36-1.26 (m, 7H), 0.96-
0.91 (dd, 6H, J = 12.5 Hz, J = 6.3 Hz); 1 3 C NMR
(100 MHz, CDCl3 ): δ 176.0, 70.6, 55.6, 53.3, 43.6,
24.84, 24.78, 24.6, 23.3, 21.3; ESI-MS(+) m/z
calcd. For C1 0 H2 3 N2 O2 [M+H]+ : 203.1754, found
[M+H]+ : 203.1754.
4.6.18. 2-(4-Methoxybenzyl)benzaldehyde (9f)1 6
1 H NMR (400 MHz, CDCl3 ): δ 10.26 (s, 1H),
7.87-7.85 (dd, 1H, J = 7.6 Hz, 1.4 Hz), 7.54-7.50