A. J. Minnaard, J. G. de Vries et al.
33.3 min (major). Characterization matched with previously reported
data.[6b,10]
J=6.7 Hz, 2H), 2.19–2.03 (m, 1H), 1.95–1.80 (m, 2H), 1.75–1.59 (m,
1H), 1.28 ppm (s, 3H); 13C NMR (101.59 MHz, CDCl3): d=211.3, 147.9,
145.8, 141.5, 118.7, 108.0, 106.4, 101.0, 53.4, 42.8, 40.8, 38.2, 30.2,
22.0 ppm; HRMS (ESI+): m/z calcd: 255.09917 [M+Na]+; found:
255.09913 [M+Na]+; chiral HPLC: Chiracel OJ-H column, n-heptane/
iPrOH 99:1, 408C, detection at l=220 nm, tR =52.4 (minor) and 62.1 min
(major).
Compound (S)-3c: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3c
was obtained as a colorless oil (96%, 97% ee). [a]2D0 =+70.5 (c=1.13 in
CHCl3). 1H NMR (400 MHz, CDCl3): d=7.23 (d, J=8.3 Hz, 2H), 7.15
(d, J=8.4 Hz, 2H), 2.88 (d, J=14.1 Hz, 1H), 2.43 (d, J=14.1 Hz, 1H),
2.33 (s, 3H), 2.23–2.14 (m, 2H), 1.99–1.82 (m, 2H), 1.76–1.59 (m, 2H),
1.32 ppm (s, 3H); 13C NMR (101.59 MHz, CDCl3): d=211.5, 147.5, 128.6,
126.2, 125.6, 53.1, 42.9, 40.8, 38.0, 29.8, 22.0 ppm; HRMS (ESI+): m/z
calcd: 225.12496 [M+Na]+; found: 225.12499 [M+Na]+; chiral GC (GTA
column): tR =38.3 (minor) and 38.8 min (major). Characterization
matched with previously reported data.[5b,6b,10]
Compound (S)-3i: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3i
was obtained as a colorless oil (88%, 99% ee). [a]2D0 =+68.2 (c=1.57 in
CHCl3); 1H NMR (400 MHz, CDCl3): d=7.36–7.21 (m, 2H), 7.03–6.98
(m, 2H), 2.85 (d, J=14.1 Hz, 1H), 2.44 (d, J=14.2 Hz, 1H), 2.32 (t, J=
6.7 Hz, 2H), 2.23–2.09 (m, 1H), 1.98–1.81 (m, 2H), 1.69 (m, 1H), 1.61
(m, 1H), 1.32 ppm (s, 3H); 13C NMR: see ref. [7c]; HRMS (ESI+): m/z
calcd: 229.10046 [M+Na]+; found: 229.09966 [M+Na]+; chiral GC (GTA
column): tR =30.5 (minor) and 30.8 min (major). Characterization
matched with previously reported data.[10]
Compound (S)-3d: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=9:1). Compound 3d
was obtained as a colorless oil (44%, 93% ee). [a]2D0 =M+ >49.1 (c=
1.45 in CHCl3); 1H NMR (400 MHz, CDCl3): d=7.21 (t, J=8.0 Hz, 1H),
6.87 (d, J=7.7 Hz, 2H), 7.03 (d, J=8.1 Hz, 1H), 4.0 (q, J=6.9 Hz, 2H),
2.85 (d, J=14.2 Hz, 1H), 2.41 (d, J=14.2 Hz, 1H), 2.30 (t, J=10.6 Hz,
2H), 2.18–2.13 (m, 1H), 1.92–1.83 (m, 2H), 1.70–1.61 (m, 1H), 1.40 (t,
J=6.7 Hz, 3H), 1.38 ppm (s, 3H); 13C NMR (101.59 MHz, CDCl3): d=
211.5, 159.1, 149.3, 129.5, 118.0, 112.8, 111.5, 63.4, 53.2, 42.9, 40.9, 38.0,
29.8 ppm; HRMS: m/z calcd: 255.13555 [M+Na]+; found: 255.13532
[M+Na]+; chiral HPLC: Chiralpak AD-H column, n-heptane/iPrOH
99:1, 408C, detection at l=210 nm, tR =21.3 (minor) and 23.2 min
(major). Characterization matched with previously reported data.[5b,6b,10]
Compound (S)-13a: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=9:1). Compound 13a
was obtained as colorless oil (93%, 93% ee). [a]2D0 =À10.8 (c=1.19 in
CHCl3); 1H NMR (400 MHz, CDCl3): d=7.36–7.13 (m, 5H), 2.61 (d, J=
17.6 Hz, 1H), 2.43 (d, J=17.5 Hz, 1H), 2.39–2.16 (m, 2H), 2.33–2.26 (m,
2H), 1.34 ppm (s, 3H); 13C NMR (101.59 MHz, CDCl3): d=218.5, 148.5,
128.6, 126.3, 125.4, 52.2, 43.8, 36.7, 35.8, 29.4 ppm; HRMS (ESI+): m/z
calcd: 197.09423 [M+Na]+; found: 197.09341 [M+Na]+; chiral GC (GTA
column): tR =16.7 (minor) and 17.2 min (major). Characterization
matched with previously reported data.[6b,10]
Compound (S)-3e: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3e
was obtained as a colorless oil (30%, 98% ee). The reaction did not pro-
ceed to completion even after 72 h. 1H NMR (400 MHz, CDCl3): d=
7.37–7.32 (m, 1H), 7.32–7.26 (m, 1H), 7.26–7.20 (m, 2H), 2.87 (d, J=
14.1 Hz, 1H), 2.47 (d, J=14.1 Hz, 1H), 2.36 (t, J=6.6 Hz, 2H), 2.26–2.11
(m, 1H), 2.03–1.85 (m, 2H), 1.80–1.66 (m, 1H), 1.34 ppm (s, 3H);
13C NMR (101.59 MHz, CDCl3): d=210.8, 149.8, 129.9, 126.5, 126.1,
123.9, 53.0, 43.0, 40.8, 37.9, 29.6, 22.1, 15.4 ppm; chiral HPLC analysis:
Chiracel OJ-H column, n-heptane/iPrOH 99:1, 408C, detection at l=
210 nm, tR =23.3 (minor) and 24.7 min (major). Characterization matched
with previously reported data.[5b,6b,10]
Compound (S)-14a: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 14a
was obtained as a colorless oil (91%, 99% ee). [a]2D0 =+73.8 (c=0.83 in
CDCl3); 1H NMR (400 MHz, CDCl3): d=7.35–7.26 (m, 4H), 7.22–7.18
(m, 1H), 2.93 (d, J=14.1 Hz, 1H), 2.43 (d, J=14.1 Hz, 1H), 2.31–2.28
(m, 2H), 2.21–2.1 (m, 1H), 2.02–1.95 (m, 1H), 1.88–1.72 (m, 2H), 1.69–
1.53 (m, 2H), 0.6 ppm (t, J=7.4 Hz, 3H); HRMS (ESI+): m/z calcd:
225.12553 [M+Na]+; found: 225.12479 [M+Na]+; chiral GC (GTA
column): tR =34.4 (minor) and 34.8 min (major). Characterization
matched with previously reported data.[6b,10]
Compound (S)-15a: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 15a
was obtained as a colorless oil (80%, 94% ee). [a]2D0 =+20.7 (c=0.27 in
CDCl3); 1H NMR (400 MHz, CDCl3): d=7.32 (d, J=4.3 Hz, 4H), 7.21–
7.18 (m, 1H), 3.20 (d, J=14.4 Hz, 1H), 2.71 (d, J=14.4 Hz, 1H), 2.44–
2.36 (m, 2H), 2.20–2.16 (m, 1H), 1.92–1.57 (m, 5H), 1.27 ppm (s, 3H);
13C NMR (101.59 MHz, CDCl3: d=213.8, 147.9, 128.6, 126.0, 125.6, 55.7,
44.2, 43.5, 39.8, 31.9, 25.8, 23.9 ppm; HRMS (ESI+): m/z calcd:
225.12499 [M+Na]+; found: 225.12484 [M+Na]+; chiral GC (GTA
column): tR =34.8 (minor) and 35.1 min (major). Characterization
matched with previously reported data.[6b,10]
Compound (S)-3 f: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3 f
was obtained as a colorless oil (98%, 99% ee). [a]2D0 =+65.4 (c=1.93 in
CHCl3); 1H NMR (400 MHz, CDCl3): d=7.35 (d, J=2.5 Hz, 1H), 7.19
(dd, J=2.5, 8.6 Hz, 1H), 6.90 (d, J=8.6 Hz, 1H), 2.83 (d, J=14.1 Hz,
1H), 2.43 (d, J=14.1 Hz, 1H), 2.33 (t, J=6.7 Hz, 2H), 2.18–2.12 (m,
1H), 1.96–1.83 (m, 2H), 1.76–1.62 (m, 1H), 1.31 ppm (s, 3H); 13C NMR
(101.59 MHz, CDCl3): d=210.9, 153.1, 140.6, 127.5, 124.9, 122.3, 111.8,
56.0, 52.9, 42.2, 40.6, 37.8, 29.8, 21.9 ppm; HRMS (ESI+): m/z calcd:
275.08093 [M+Na]+; found: 275.08096 [M+Na]+; chiral HPLC: Chiracel
OJ-H column, n-heptane/iPrOH 99:1, 408C, detection at l=200 nm, tR =
51.2 (minor) and 59.3 min (major).
Compound (S)-16a: Synthesized according to the general procedure with
boronic acid (3 equiv) and purified by flash chromatography (n-pentane/
EtOAc=7:2). Compound 16a was obtained as a colorless oil (57%,
Compound (S)-3g: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3g
was obtained as a colorless oil (85%, 98% ee). [a]2D0 =+68.1 (c=1.65 in
CHCl3); 1H NMR (400 MHz, CDCl3): d=7.24 (d, J=8.6 Hz, 2H), 6.86
(d, J=8.6 Hz, 2H), 3.79 (s, 3H), 2.85 (d, J=14.1 Hz, 1H), 2.42 (d, J=
14.2 Hz, 1H), 2.30 (t, J=6.7 Hz, 2H), 2.21–2.10 (m, 1H), 1.94–1.82 (m,
2H), 1.71–1.60 (m,1H), 1.30 ppm (s, 2H); 13C NMR (101.59 MHz,
CDCl3): d=211.7, 157.7, 139.4, 126.7, 113.8, 55.2, 53.3, 42.3, 40.8, 38.1,
30.1, 22.0 ppm; HRMS (ESI+): m/z calcd: 241.11990 [M+Na]+, found:
241.11961 [M+Na]+; chiral HPLC: Chiracel OJ-H column, n-heptane/
iPrOH 99:1, 408C, detection at l=225 nm, tR =52.72 (minor) and
57.04 min (major). Characterization matched with previously reported
data.[5b,6b,10]
1
88% ee). [a]2D0 =+100.0 (c=0.11 in CHCl3); H NMR (400 MHz, CDCl3):
d=7.34 (t, J=7.6 Hz, 2H), 7.30–7.20 (m, 3H), 4.41–4.27 (m, 1H), 4.15–
3.97 (m, 1H), 3.00 (dd, J=1.3, 17.2 Hz, 1H), 2.57 (d, J=17.2 Hz, 1H),
2.17–2.14 (m, 1H), 2.09–2.02 (m, 1H), 1.40 ppm (s, 3H); 13C NMR
(101.59 MHz, CDCl3): d=170.9, 145.6, 129.0, 126.9, 125.2, 66.8, 42.9, 37.3,
36.4, 29.8 ppm; HRMS (ESI+): m/z calcd: 213.0891 [M+Na]+; found:
213.08838 [M+Na]+; chiral HPLC: Chiralpak AS-H column, n-heptane/
iPrOH 90:10, 408C, detection at l=210 nm, tR =27.1 (major) and
30.5 min (minor). Characterization matched previously reported data.[7b]
Compound (S)-17a: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/EtOAc=8:1). Compound
17a was obtained as a colorless oil (28%, 69% ee). [a]2D0 =+78.6 (c=0.35
1
Compound (S)-3h: Synthesized according to the general procedure and
purified by flash chromatography (n-pentane/Et2O=4:1). Compound 3h
was obtained as a colorless oil (98%, 96% ee). [a]2D0 =+73.5 (c=0.80 in
CHCl3); 1H NMR (400 MHz, CDCl3): d=6.82 (s, 1H), 6.74 (brs, 2H),
5.93 (s, 2H), 2.81 (d, J=14.2 Hz, 1H), 2.40 (d, J=14.2 Hz, 1H), 2.30 (t,
in CHCl3); H NMR (400 MHz, CDCl3): d=7.42–7.34 (m, 4H), 7.30–7.24
(m, 1H), 4.03 (ddd, J=3.5, 6.9, 11.6 Hz, 1H), 3.67 (ddd, J=4.1, 10.1,
11.7 Hz, 1H), 3.11 (dd, J=1.7, 14.4 Hz, 1H), 2.69 (dd, J=1.0, 14.4 Hz,
1H), 2.61–2.49 (m, 1H), 2.24 (dtd, J=1.8, 3.8, 14.6 Hz, 1H), 1.57 ppm (s,
3H); 13C NMR (101.59 MHz, CDCl3): d=206.5, 143.5, 128.6, 127.5, 125.8,
&
6
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Chem. Eur. J. 0000, 00, 0 – 0
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