F. Le6rat et al. / Tetrahedron: Asymmetry 13 (2002) 2335–2344
2343
1
2
(
2 mg, 96% with mp 160°C (decomp.). H NMR
(Ph), 125.69 (Ph), 127.38 (Ph), 132.13 (Ph), 143.36 (Ph),
3
19
CDCl , 500.13 MHz): l 1.62–1.64 (d, J(H,H)=7.0,
H, CH-CH ), 2.96 (d, J(H,H)=1.3, 3H, N(CH ) ),
.01–3.04 (m, 4H, N(CH ) and NH ), 3.76–3.82 (m,
H, CH-CH ), 4.11–4.15 (q, J(H,F)=7.0, CH-CF ),
.36–4.39 (m, 1H, NH ), 6.80–6.82 (m, 1H, Ph), 7.01–
.10 (m, 3H, Ph). C NMR (CDCl , 125.75 MHz): l
7.88 (N(CH ) ), 53.50 (N(CH ) ), 56.35 (CH-CH ),
8.15–78.79 (q, J(C,F)=27, CH-CF ), 120.83–127.63
q, J(C,F)=285, CF ), 125.11 (Ph), 125.65 (Ph), 127.37
Ph), 132.62 (Ph), 143.25 (Ph), 145.59 (Ph), 181.42
CꢀO). F NMR (CDCl , 470.50 MHz): l −64.61.
MS-FAB (NOBA): m/z 703.8 ([2M−Ala] ), 396.9 ([M] ),
145.67 (Ph), 179.78 (CꢀO). F NMR (CDCl , 470.50
3
3
4
3
3
1
4
7
4
7
(
(
(
MHz): l −64.57. MS-FAB (NOBA): m/z 734.0 ([2M−
3
3 2
+
+
+
Val] ), 425.0 ([M] ), 382.0, 307.0 ([M−Val] ).
3
2
2
3
3
3
4.4.12. Synthesis of {[(R)-phenylalaninato-N,O][(S)-
N,N-dimethyl-(2,2,2-trifluoro-1-phenylethyl)amine-C,N]-
palladium(II)}. (R)-Phenylalanine (14 mg, 0.09 mmol,)
and potassium carbonate (13 mg, 0.09 mmol) were
dissolved in 2 ml water. cis/trans-(S,S)-1 (15 mg, 0.02
mmol) was added and the mixture was stirred for 24 h
at rt. The yield after work-up (see general procedure)
2
13
3
3
2
3 2
3
2
3
1
3
1
9
3
+
+
1
was 20 mg, 97% with mp 125°C (decomp.). H NMR
+
3
06.9 ([M−Ala] ).
(CD Cl , 360.13 MHz): l 2.67–2.69 (m, 1H, NH ), 2.90
2
2
2
(
s, 3H, N(CH ) ), 2.94 (s, 3H, N(CH ) ), 3.26–3.33 (m,
3 2 3 2
4
.4.10. Synthesis of {[(R)-prolinato-N,O][(S)-N,N-
1H, CH-CH -Ph), 3.42–3.47 (m, 1H, CH-CH -Ph),
2
2
dimethyl - (2,2,2 - trifluoro - 1 - phenylethyl)amine - C,N]-
palladium(II)}. (R)-Proline (13 mg, 0.12 mmol,) and
potassium carbonate (16 mg, 0.12 mmol) were dissolved
in water (2 ml). cis/trans-(S,S)-1 (20 mg, 0.03 mmol)
was added and the mixture was stirred for 9 h at rt. The
3.75–3.81 (m, 1H, CH-CH -Ph), 3.94–4.00 (q,
2
3
J(H,F)=7, CH-CF ), 4.29–4.33 (m, 1H, NH ), 6.59–
3
2
6.61 (m, 1H, Ph), 6.96–7.00 (m, 1H, Ph), 7.04–7.10 (m,
13
2H, Ph), 7.25–7.34 (m, 5H, Ph(Phe)). C NMR
(CD Cl , 90.55 MHz): l 41.28 (CH-CH -Ph), 47.97
2
2
2
yield after work-up (see general procedure) was 24 mg,
(N(CH ) ), 53.37 (N(CH3)2), 62.22 (CH-CH -Ph),
3
2
2
1
2
9
5
6%, with mp of 180°C (decomp.). H NMR (CD Cl ,
77.76–78.63 (q, J(C,F)=26, CH-CF ), 120.12–129.57
2
2
3
1
00.13 MHz): l 1.68–1.74 (m, 1H, CH (NH)-CH -CH -
(q, J(C,F)=285, CF ), 125.51 (Ph), 125.86–125.89 (q,
J(C,F)=2.7, Ph), 127.58 (Ph), 128.16 (Ph(Phe)),
2
2
2
3
4
CH(CO )), 1.92–1.99 (m, 1H, CH (NH)-CH -CH -
2
2
2
2
CH(CO )), 2.15–2.20 (m, 2H, CH (NH)-CH -
129.90 (Ph(Phe)), 130.19 (Ph(Phe)), 132.87 (Ph), 137.51
2
2
2
CH -CH(CO )), 2.91 (s, 3H. N(CH ) ), 2.93–2.94 (m,
(Cquat.), 143.83 (Cquat.), 145.88 (Cquat.), 179.58 (CꢀO).
2
2
3 2
1
9
3
H, N(CH ) ), 3.21–3.34 (m, 2H, CH (NH)-CH -CH -
F NMR (CD Cl , 470.50 MHz): l −64.01. MS-FAB
2 2
+ +
3
2
2
2
2
CH(CO )), 4.01–4.08 (m, 2H, CH (NH)-CH -CH -
(NOBA): m/z 782.0 ([2M−Phe] ), 473.0 ([M] ), 429.0,
308.0 ([M−Phe] ).
2
2
2
2
+
CH(CO ) and CH-CF ), 4.34–4.38 (m, 1H, NH),
2
3
.98–7.01 (m, 1H, Ph), 7.03–7.06 (m, 2H, Ph), 7.10–7.12
13
4.4.13. Synthesis of {[(R)-leucinato-N,O][(S)-N,N-
dimethyl - (2,2,2 - trifluoro - 1 - phenylethyl)amine - C,N]-
palladium(II)}. (R)-Leucine (11 mg, 0.09 mmol) and
potassium carbonate (13 mg, 0.09 mmol) were dissolved
in 2 ml water. cis/trans-(S,S)-1 (15 mg, 0.02 mmol) was
added and the mixture was stirred for 20 h at rt. The
2
2
(
CH (NH)-CH -CH -CH(CO )), 30.56 (CH (NH)-CH -
2
2
2
2
2
2
CH -CH(CO )), 48.31 (N(CH ) ), 53.59 (CH (NH)-
2
2
3 2
2
CH -CH -CH(CO )),
53.91
(N(CH3)2),
65.93
(q,
2
2
2
(
CH (NH)-CH -CH -CH(CO )),
J(C,F)=27, CH-CF ), 120.75–127.50 (q, J(C,F)=
78.83–79.47
2
2
2
2
2
1
3
2
83, CF ), 124.61 (Ph), 125.87 (Ph), 127.27 (Ph), 133.19
yield after work-up (see general procedure) was 19 mg,
3
19
1
(
Ph), 143.41 (Ph), 147.79 (Ph), 180.76 (CꢀO). F NMR
100% with mp 170°C (decomp.). H NMR (CDCl ,
3
3
(CD Cl , 470.50 MHz): l −67.26. MS-FAB (NOBA):
360.13 MHz): l 0.96–0.98 (d, J(H,H)=6.8, 3H, CH-
CH -CH(CH ) ), 1.01–1.02 (d, J(H,H)=6.4, 3H, CH-
2
2
+
+
+
3
m/z 843.8 ([2M] ), 731.8 ([2M−Pro] ), 422.9 ([M] ),
2
3 2
+
3
76.9, 306.9 ([M−Pro] ).
CH -CH(CH ) ), 1.74–1.92 (m, 2H,, CH-CH2-
2 3 2
CH(CH ) ), 2.01–2.08 (m, 1H,, CH-CH -CH(CH ) ),
3
2
2
3 2
4
.4.11. Synthesis of {[(R)-valinato-N,O][(S)-N,N-
2.65–2.67 (m, 1H, NH ), 2.97 (s, 3H, N(CH ) ), 3.05 (s,
2 3 2
dimethyl - (2,2,2 - trifluoro - 1 - phenylethyl)amine - C,N]-
palladium(II)}. (R)-Valine (14 mg, 0.12 mmol) and
potassium carbonate (16 mg, 0.12 mmol) were dissolved
in 2 ml water. cis/trans-(S,S)-1 (20 mg, 0.03 mmol) was
added and the mixture was stirred for 20 h at rt. The
3H, N(CH ) ), 3.68–3.73 (m, 1H, CH-CH -CH(CH ) ),
3
2
2
3 2
3
4.07–4.13 (q, J(H,F)=7, 1H, CH-CF ), 4.20–4.24 (m,
3
1H, NH ), 6.73–6.75 (m, 1H, Ph), 7.01–7.12 (m, 3H,
2
13
Ph). C NMR (CDCl , 90.55 MHz): l 22.09 (CH-CH -
3
2
CH(CH ) ), 23.58 (CH-CH -CH(CH ) ), 25.29 (CH-
3
2
2
3 2
yield after work-up (see general procedure) was 22 mg,
CH -CH(CH ) ), 44.20 (CH-CH -CH(CH ) ), 47.97
2 3 2 2 3 2
1
8
5
9% with mp of 125°C (decomp.). H NMR (CDCl ,
(N(CH3)2), 53.54 (N(CH ) ), 59.05 (CH-CH2-
3
3 2
2
3
00.13 MHz): l 1.18–1.19 (d, J(H,H)=6.9, 3H, CH-
CH(CH ) ), 78.01–78.96 (q, J(C,F)=26, CH-CF3),
3
2
3
1
CH(CH ) ), 1.21–1.22 (d, J(H,H)=7.0, 3H, CH-
119.49–128.94 (q, J(C,F)=285, CF ), 125.21 (Ph),
3
2
3
CH(CH ) ), 2.45–2.51 (m, 1H,4 CH-CH(CH3)2),
125.76 (Ph), 127.40 (Ph), 132.23 (Ph), 143.34 (Ph),
3
2
19
2
.57–2.59 (m, 1H, NH ), 2.96 (d, J(H,H)=1.5, 3H,
145.57 (Ph), 181.00 (CꢀO). F NMR (CDCl , 470.50
2
3
N(CH ) ), 3.01 (s, 3H, N(CH ) ), 3.53–3.55 (m, 1H,
MHz): l −64.70. MS-FAB (NOBA): m/z 748.0 ([2M−
3
2
3 2
3
+
+
+
CH-CH(CH ) ), 3.99–4.03 (q, J(H,F)=7, CH-CF3),
Leu] ), 439.0 ([M] ), 394.0, 307.9 ([M−Leu] ).
3
2
4
7
1
.32–4.36 (m, 1H, NH ), 6.76–6.81 (m, 1H, Ph), 7.03–
2
1
3
.11 (m, 3H, Ph). C NMR (CDCl , 125.75 MHz): l
4.4.14. Synthesis of {[(R)-isoleucinato-N,O][(S)-N,N-
dimethyl - (2,2,2 - trifluoro - 1 - phenylethyl)amine - C,N]-
palladium(II)}. (R)-Isoleucine (11 mg, 0.09 mmol,) and
potassium carbonate (13 mg, 0.09 mmol) were dissolved
in 2 ml water. cis/trans-(S,S)-1 (15 mg, 0.02 mmol) was
3
8.13 (CH-CH(CH ) ), 19.92 (CH-CH(CH ) ), 31.87
3
2
3 2
(
CH-CH(CH ) ), 47.96 (N(CH ) ), 53.36 (N(CH ) ),
5.75 (CH-CH(CH ) ), 77.91–78.54 (q, J(C,F)=26,
3 2
1
3
2
3 2
3 2
2
6
CH-CF ), 120.83–127.62 (q, J(C,F)=284, CF ), 125.23
3
3