Molecules 2017, 22, 1748
10 of 14
N-((2S,3S)-1-(3,4-Dimethylphenyl)-3-methyl-1-oxopentan-2-yl)-2,2,2-trifluoroacetamide (TFA
-
L
-
Ile
-
Ph(3,4
-
Me)
,
.
L
-
1f): Colorless needles. [
1H-NMR (270 MHz, CDCl3)
4.1 Hz, 1H, CHNH), 2.35 (s, 6H, 2
1.08–0.93 (m, 4H, overlap CH2CH3 and CHCH3), 0.81 (t, J = 7.4 Hz, 3H, CH2CH3) ppm. 13C-NMR (67.5
α] = +82 (c 1.0, CHCl3). IR (neat) ν
: 3343, 3075, 2979, 1742, 1691 cm−1
D
δ
: 7.71 (d, J = 11.2 Hz, 2H, Ar-H), 7.29 (s, 1H, Ar-H), 5.56 (dd, J = 8.7,
CH3), 2.06–1.95 (m, 1H, CHCH3), 1.40–1.26 (m, 1H, CH2CH3),
×
MHz, CDCl3) δ =
: 197.2, 157.1 (q, 2JCF = 37.2 Hz), 144.3, 137.6, 132.5, 130.2, 129.7, 126.5, 115.9 (q, 1JCF
287.9 Hz), 58.3, 38.9, 23.7, 20.1, 19.8, 16.2, 11.4 ppm. HRMS-ESI (m/z) [M + H]+ calcd for C16H21F3NO2
316.1524, found 316.1506.
N-((2S,3S)-1-(2,4-Dimethylphenyl)-3-methyl-1-oxopentan-2-yl)-2,2,2-trifluoroacetamide (TFA
1g): Colorless needles. [ = +49 (c 0.25, CHCl3). IR (neat)
: 3294, 3097, 2969, 1714, 1685 cm−1
1H-NMR (270 MHz, CDCl3)
-
L
-
Ile
-
Ph(2,4
-
Me)
,
.
L
-
α
]
δ
ν
D
: 7.63 (d, J = 8.6 Hz, 1H, Ar-H), 7.14-7.02 (m, 2H, Ar-H), 5.49 (dd, J = 8.4,
4.1 Hz, 1H, CHNH), 2.49 (s, 3H, CH3), 2.38 (s, 3H, CH3), 1.99–1.87 (m, 1H, CHCH3), 1.32–1.19 (m, 1H,
CH2CH3), 1.07–0.87 (m, 4H, overlap CH2CH3 and CHCH3), 0.81 (t, J = 7.3 Hz, 3H, CH2CH3) ppm.
13C-NMR (67.5 MHz, CDCl3) : 199.9, 157.1 (q, 2JCF = 37.4 Hz), 143.2, 139.5, 133.3, 132.2, 129.4, 126.6,
δ
115.9 (q, 1JCF = 288.3 Hz), 59.8, 38.5, 24.1, 21.2, 21.0, 15.9, 11.2 ppm. HRMS-ESI (m/z) [M + H]+ calcd
for C16H21F3NO2 316.1524, found 316.1526.
N-((2S,3S)-1-(2,5-Dimethylphenyl)-3-methyl-1-oxopentan-2-yl)-2,2,2-trifluoroacetamide (TFA
1h): Colorless needles. [ = +68 (c 1.0, CHCl3). IR (neat)
1H-NMR (270 MHz, CDCl3)
-
L
-
Ile
-
Ph(2,5
-
Me)
,
.
−1
L
-
α
]
ν: 3302, 3024, 2934, 1714, 1686, 1567 cm
: 7.5 (s, 1H, Ar-H), 7.3 (d, J = 7.6 Hz, 1H, Ar-H), 7.2 (d, J = 7.6 Hz, 1H,
D
δ
Ar-H), 5.5 (dd, J = 8.6, 4.0 Hz, 1H, CHNH), 2.4 (s, 3H, CH3), 2.4 (s, 3H, CH3), 2.0–1.8 (m, 1H, CHCH3),
1.4–1.2 (m, 1H, CH2CH3), 1.1–0.9 (m, 3H overlap CH2CH3 and CHCH3), 0.8 (t, J = 7.3 Hz, 3H, CH2CH3)
ppm. 13C-NMR (67.5 MHz, CDCl3) : 200.7, 157.1 (q, 2JCF = 37.2 Hz), 135.9, 135.6, 135.0, 133.3, 132.3,
δ
129.3, 115.9 (q, 1JCF = 287.9 Hz), 60.1, 38.4, 24.1, 20.7, 20.3, 15.9, 11.3 ppm. HRMS-ESI (m/z) [M + H]+
calcd for C16H21F3NO2 316.1524, found 316.1530.
2,2,2-Trifluoro-N-((2S,3R)-3-methyl-1-oxo-1-phenylpentan-2-yl)acetamide (TFA
needles. [ = +79 (c 2.0, CHCl3). IR (neat)
: 3335, 3068, 2971, 1741, 1693 cm−1. H-NMR (270 MHz,
CDCl3) : 7.98 (d, J = 7.6 Hz, 2H, Ar-H), 7.65 (t, J = 7.6 Hz, 1H, Ar-H), 7.53 (t, J = 7.6 Hz, 2H, Ar-H), 5.74
-L-allo-Ile-Ph, L-2c): Colorless
1
α
]
ν
D
δ
(dd, J = 8.9, 3.0 Hz, 1H, CHNH), 2.09–1.94 (m, 1H, CHCH3), 1.62–1.49 (m, 1H, CH2CH3), 1.38–1.21 (m,
1H, CH2CH3), 1.06 (t, J = 7.3 Hz, 3H, CH2CH3), 0.76 (d, J = 6.9 Hz, 3H, CHCH3) ppm. 13C NMR (67.5
MHz, CDCl3)
δ
: 197.1, 157.3 (q, 2JCF = 37.1 Hz), 134.4, 134.0, 129.1 (2
×
CH), 128.7 (2
×
CH), 115.9 (q,
1JCF = 287.7 Hz), 57.1, 38.7, 27.3, 13.4, 12.0 ppm. HRMS-ESI (m/z) [M + Na]+ calcd for C14H16F3NO2Na
310.1031, found 310.1039.
2,2,2-Trifluoro-N-((2R,3S)-3-methyl-1-oxo-1-phenylpentan-2-yl)acetamide (TFA
needles. [ 79 (c 2.0, CHCl3). IR (neat)
: 3331, 3067, 2969, 1738, 1692 cm−1. H-NMR (270 MHz,
CDCl3) : 7.98 (d, J = 7.4 Hz, 2H, Ar-H), 7.66 (t, J = 7.4 Hz, 1H, Ar-H), 7.53 (t, J = 7.4 Hz, 2H, Ar-H), 5.74
-D-allo-Ile-Ph, D-2c): Colorless
1
α
]
D
=
−
ν
δ
(dd, J = 8.7, 2.8 Hz, 1H, CHNH), 2.07–1.94 (m, 1H, CHCH3), 1.66–1.48 (m, 1H, CH2CH3), 1.38–1.21 (m,
1H, CH2CH3), 1.06 (t, J = 7.3 Hz, 3H, CH2CH3), 0.76 (d, J = 6.9 Hz, 3H, CHCH3) ppm. 13C-NMR (67.5
MHz, CDCl3)
δ
: 197.1, 157.3 (q, 2JCF = 37.4 Hz), 134.4, 134.1, 129.1 (2
×
CH), 128.7 (2
×
CH), 115.9 (q,
1JCF = 287.9 Hz), 57.1, 38.7, 27.3, 13.4, 12.0 ppm. HRMS-ESI (m/z) [M + Na]+ calcd for C14H16F3NO2Na
310.1031, found 310.1040.
2,2,2-Trifluoro-N-(2-oxo-2-phenylethyl)acetamide (TFA
-
Gly
-
Ph
, 3c) [2]: Colorless oil. IR (neat) ν: 3327,
1
3103, 2927, 1733, 1703 cm−1. H-NMR (270 MHz, CDCl3)
δ
: 7.99 (d, J = 7.4 Hz, 2H, Ar-H), 7.68 (t, J =
7.4 Hz, 1H, Ar-H), 7.54 (t, J = 7.4 Hz, 2H, Ar-H), 4.83 (d, J = 4.3 Hz, 2H, CH2NH) ppm. 13C NMR (67.5
MHz, CDCl3) CH), 127.9 (2 CH), 115.7 (q,
: 192.1, 157.1 (q, 2JCF = 37.6 Hz), 134.6, 133.6, 129.1 (2
1JCF = 287.3 Hz), 46.1 ppm. HRMS-ESI (m/z) [M + H]+ calcd for C10H9F3NO2 232.0585, found 232.0595.
δ
×
×
(S)-2,2,2-trifluoro-N-(1-oxo-1-phenylpropan-2-yl)acetamide (TFA
7.0 (c 1.0, CHCl3). Lit. [26] [ 8.6 (c 0.17, CHCl3). IR (neat)
1H-NMR (270 MHz, CDCl3)
-
L
-
Ala
-
Ph
,
L
-
4c) [
,
,
−1
=
−
α
]
D
=
−
ν
: 3331, 3070, 2991, 1738, 1701 cm
.
δ
: 7.99 (d, J = 7.4 Hz, 2H, Ar-H), 7.67 (t, J = 7.4 Hz, 1H, Ar-H), 7.54 (t, J = 7.4