([M + NH4]+, C25H28NO5S+; calc. 454.1683). Anal. calc. for C25H24O5S: C 68.79, H 5.54, O 18.33; found: C
68.64, H 5.58, O 18.17.
4-Methoxybenzyl 2-(((4-methoxyphenyl)thio)carbonyl)pent-4-enoate (4i). According to general
method A on a 0.18 mmol scale with 1.5 equiv. 4-methoxybenzyl-2,2,2-trichloroacetimidate, the
product was obtained as a colorless oil (60 mg, 86% yield). Analytical data: FT-IR (neat): 2955 (br, C-
H arom. and C-H aliph.), 1737 (C=O). 1699 (C=O). 1H-NMR (300 MHz, CDCl3, 298 K): 7.38-7.23 (4 H, m,
ArH), 6.98-6.87 (4 H, m, ArH), 5.79 (1 H, ddt, 3JHH = 17.0 Hz, 3JHH = 10.0 Hz, 3JHH = 7.0 Hz, CHCH2CHCH2),
5.23-5.03 (2 H, m, CHCH2CHCH2), 5.16 (2 H, s, ArCH2), 3.84 (3 H, s, OCH3), 3,83 (3 H, s, OCH3), 3.78 (1
H, t, 3JHH = 7.5 Hz, CHCH2CHCH2), 2.99-2.42 (2 H, m, CHCH2CHCH2). 13C-NMR (100 MHz, CDCl3, 298 K):
193.4 (C=O), 168.0 (C=O), 161.0 (Ar), 159.8 (Ar), 136.1 (ArH), 133.5 (CH), 130.2 (ArH), 127.5 (Ar),
118.1 (CH2), 117.5 (Ar), 115.0 (ArH), 113.9 (ArH), 67.3 (ArCH2), 58.9 (CH), 55.4 (OCH3), 55.3 (OCH3),
33.4 (CH2). HR-ESI-MS (pos.): 404.1527 ([M + NH4]+, C21H26NO5S+; calc. 404.1526). Anal. calc. for
C21H22O5S: C 65.27, H 5.74, O 20.70; found: C 65.40, H 5.81, O 20.97.
4-Methoxybenzyl 2-fluoro-3-((4-methoxyphenyl)thio)-3-oxopropanoate (4j). According to general
method A on a 4.09 mmol scale with 4-methoxybenzyl-2,2,2-trichloroacetimidate (1.2 equiv.), the
product was obtained as a colorless oil (1.40 g, 94% yield). Analytical data: FT-IR (neat): 2958 (br, C-
H arom. and C-H aliph.), 1752 (C=O). 1699 (C=O). 1H-NMR (300 MHz, CDCl3, 298 K): 7.53-7.14 (4 H, m,
2
ArH), 7.07-6.80 (4 H, m, ArH), 5.43 (1 H, d, JHF = 48.5 Hz, C(F)H, 5.26 (2 H, s, ArCH2), 3.85 (3 H, s,
OCH3), 3.83 (3 H, s, OCH3). 13C-NMR (100 MHz, CDCl3, 298 K): 191.5 (d, 2JCF = 28.0 Hz, C=O), 163.2 (d,
2JCF = 24.5 Hz, C=O), 161.2 (Ar), 160.0 (Ar), 136.3 (ArH), 130.4 (ArH), 126.5 (Ar), 115.2 (ArH), 115.1 (d,
4JCF = 4.5 Hz, Ar), 114.1 (ArH), 90.8 (d, 1JCF = 202.0 Hz, CF), 68.3 (CH2), 55.4 (OCH3). 19F-NMR (377 MHz,
2
CDCl3, 298 K): −192.2 (d, JHF = 48.5 Hz). HR-MALDI-MS (pos.): 387.0675 ([M + Na]+, C18H17FO5SNa+;
calc. 387.0673). Anal. calc. for C18H17FO5S: C 59.33, H 4.70; found: C 59.19, H 4.76.
tert-Butyl 3-((4-methoxyphenyl)thio)-2-methyl-3-oxopropanoate (4k). According to general method
A on a 0.20 mmol scale with tert-butyl-2,2,2-trichloroacetimidate (1.2 equiv.), the product was
obtained as a colorless oil (56 mg, 91% yield). Analytical data: FT-IR (neat): 2937 (br, C-H arom. and
C-H aliph.), 1734 (C=O). 1699 (C=O). 1H-NMR (300 MHz, CDCl3, 298 K): 7.38-7.31 (2 H, m, ArH), 7.00-
6.91 (2 H, m, ArH), 3.84 (3 H, s, OCH3), 3.66 (1 H, q, 3JHH = 7.0 Hz, CHCH3), 1.51 (9 H, s, O(CH3)3), 1.46
(3 H, d, 3JHH = 7.0 Hz, CHCH3). 13C-NMR (100 MHz, CDCl3, 298 K): 195.3 (C=O), 168.4 (C=O), 160.8 (Ar),
136.1 (ArH), 117.8 (Ar), 114.9 (ArH), 82.1 (C), 55.4 (OCH3), 54.5 (CH), 27.9 (CH3), 14.0 (CH3). HR-ESI-
MS (pos.): 319.0979 ([M + Na]+, C15H20O4SNa+; calc. 319.0975). Anal. calc. for C15H20O4S: C 60.79, H
6.80, O 21.59; found: C 60.90, H 6.80, O 21.80.
Allyl 2-fluoro-3-((4-methoxyphenyl)thio)-3-oxopropanoate (4l). According to general method A on a
0.88 mmol scale with allyl-2,2,2-trichloroacetimidate (2 equiv.), the product was obtained as a
colorless oil (163 mg, 65% yield). Analytical data: FT-IR (neat): 2945 (br, C-H arom. and C-H aliph.),
1755 (C=O). 1699 (C=O). 1H-NMR (300 MHz, CDCl3, 298 K): 7.38-7.29 (2 H, m, ArH), 7.00-6.93 (2 H, m,
ArH), 5.92 (1 H, ddt, 3JHH = 17.0 Hz, 3JHH = 10.5 Hz, 3JHH = 6.0 Hz, OCH2CHCH2), 5.43 (1 H, d, 2JHF = 48.5
3
3
3
Hz, CHF), 5.38 (1 H, dq, JHH = 17.0 Hz, JHH = 1.5 Hz, OCH2CHCHH), 5.30 (1 H, dq, JHH = 10.5 Hz,
3JHH = 1.5 Hz, OCH2CHCHH), 4.84-4.70 (2 H, m, OCH2CHCH2), 3.83 (3 H, s, OCH3). C-NMR (100 MHz,
CDCl3, 298 K): 191.6 (d, JCF = 28.0 Hz, C=O), 163.1 (d, JCF = 24.5 Hz, C=O), 161.4 (Ar), 136.4 (ArH),
13
2
2
4
1
130.7 (CH), 119.8 (CH2), 115.4 (ArH), 115.2 (d, JCF = 5.0 Hz, Ar), 90.9 (d, JCF = 201.5 Hz, CF), 67.3
(CH2), 55.5 (OCH3). 19F-NMR (377 MHz, CDCl3, 298 K): −192.8 (d, JHF = 48.5 Hz). HR-EI-MS (pos.):
2
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