The Journal of Organic Chemistry
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6.72 (s, 1H), 3.57−3.49 (m, 1H), 3.46−3.37 (m, 1H), 2.33 (dd, 3JHH
11.9 and 3.9 Hz, 1H), 2.25 (s, 3H), 2.04−1.90 (m, 2H), 1.09 (t, 3JHH
=
=
11.7 min [minor enantiomer]. 94% ee. [α]25 = +19.8 (c 0.96,
D
CHCl3). 1H NMR (CDCl3): δ 7.52 (dd, 3JHH = 7.9 Hz and 4JHH = 1.2
Hz, 1H), 7.49−7.44 (m, 2H), 7.41−7.37 (m, 1H), 7.37−7.32 (m, 2H),
5.2 Hz, 1H), 0.25 (s, 3H), 0.18 (s, 3H). 13C NMR (CDCl3): δ 142.1,
137.7, 137.5, 134.3, 129.2, 128.9, 128.1, 127.7, 125.7, 125.0, 62.3, 32.6,
32.3, 21.6, −3.9, −5.3. HRMS (ESI-TOF): calcd for C18H24OSiNa (M
+ Na+) 307.1489, found 307.1485.
3
4
7.18 (td, JHH = 7.6 Hz and JHH = 1.2 Hz, 1H), 6.99−6.92 (m, 2H),
3.46 (ddd, 2JHH = 10.6 Hz and 3JHH = 7.4 and 4.3 Hz, 1H), 3.36 (ddd,
2JHH = 10.5 Hz and 3JHH = 7.8 and 6.8 Hz, 1H), 3.11 (dd, 3JHH = 12.3
and 3.4 Hz, 1H), 2.06−1.98 (m, 1H), 1.98−1.88 (m, 1H), 1.22 (bs,
1H), 0.29 (s, 3H), 0.23 (s, 3H). 13C NMR (CDCl3): δ 142.3, 137.0,
134.3, 133.0, 129.4, 128.0, 127.9, 127.5, 126.3, 125.6, 61.9, 33.3, 30.6,
−3.6, −5.5. HRMS (ESI-TOF): calcd for C17H21BrOSiNa (M + Na+)
371.0437, found 371.0431.
Table 2, Entry 5 ((S)-3e). Colorless oil, 84% yield (90.3 mg, 3e/4e
= 97/3). [α]20 = +11.0 (c 1.32, CHCl3). The absolute configuration
D
was assigned by analogy with entry 1. 1H NMR (CDCl3): δ 7.39−7.33
3
(m, 3H), 7.33−7.27 (m, 2H), 7.10 (t, JHH = 7.8 Hz, 1H), 6.78−6.73
3
(m, 1H), 6.62−6.56 (m, 2H), 6.09 (dt, JHH = 16.9 and 9.9 Hz, 1H),
3
2
5.05 (s, 2H), 4.96 (dd, JHH = 10.1 Hz and JHH = 1.4 Hz, 1H), 4.91
(dt, 3JHH = 16.9 Hz and JHH = 1.2 Hz, 1H), 3.44 (s, 3H), 3.13 (d, 3JHH
= 9.6 Hz, 1H), 0.28 (s, 3H), 0.26 (s, 3H). 13C NMR (CDCl3): δ 157.3,
143.5, 137.6, 136.8, 134.5, 129.3, 129.2, 127.6, 121.2, 115.6, 113.3,
112.8, 94.5, 56.0, 44.5, −4.3, −4.7. HRMS (ESI-TOF): calcd for
C19H24O2SiNa (M + Na+) 335.1438, found 335.1430.
Table 2, Entry 8 ((S)-3h). Colorless oil, 96% yield (86.9 mg, 3h/
4h > 99/1). [α]25 = +44.7 (c 1.10, CHCl3). The absolute
D
configuration was assigned by analogy with entry 1. 1H NMR
3
4
(CDCl3): δ 7.76 (dd, JHH = 7.9 Hz and JHH = 0.8 Hz, 1H), 7.66 (d,
3JHH = 8.3 Hz, 2H), 7.44−7.33 (m, 6H), 7.33−7.28 (m, 2H), 7.07 (dd,
3JHH = 8.4 Hz and JHH = 1.7 Hz, 1H), 6.21 (ddd, JHH = 16.8, 10.1,
4
3
and 9.5 Hz, 1H), 5.00 (ddd, 3JHH = 10.2 Hz, 2JHH = 1.7 Hz, and 4JHH
=
(S)-5e. Colorless oil, 72% yield (59.8 mg). The ee was determined
on a Daicel Chiralcel OD-H column with hexane/2-propanol = 95/5,
flow = 1.0 mL/min. Retention times: 14.4 min [major enantiomer],
0.8 Hz, 1H), 4.96 (ddd, 3JHH = 16.8 Hz, 2JHH = 1.7 Hz, and 4JHH = 1.1
Hz, 1H), 3.32 (d, 3JHH = 9.6 Hz, 1H), 0.29 (s, 3H), 0.28 (s, 3H). 13C
NMR (CDCl3): δ 139.5, 137.8, 136.8, 134.5, 133.8, 131.6, 129.4,
127.67, 127.66, 127.4, 127.2, 125.9, 125.3, 124.9, 113.4, 44.6, −4.1,
−4.6. HRMS (ESI-TOF): calcd for C21H22SiNa (M + Na+) 325.1383,
found 325.1387.
19.2 min [minor enantiomer]. 90% ee. [α]25 = −10.2 (c 0.88,
D
CHCl3). 1H NMR (CDCl3): δ 7.42−7.29 (m, 5H), 7.11 (t, 3JHH = 7.8
Hz, 1H), 6.79−6.74 (m, 1H), 6.64−6.56 (m, 2H), 5.07 (s, 2H), 3.60−
3.50 (m, 1H), 3.49−3.39 (m, 1H), 3.45 (s, 3H), 2.36 (dd, 3JHH = 11.7
and 4.1 Hz, 1H), 2.05−1.89 (m, 2H), 1.12 (t, 3JHH = 5.4 Hz, 1H), 0.27
(s, 3H), 0.20 (s, 3H). 13C NMR (CDCl3): δ 157.3, 144.1, 137.3, 134.2,
129.23, 129.17, 127.8, 121.7, 116.1, 112.7, 94.6, 62.2, 56.0, 32.8, 32.3,
−4.0, −5.3. HRMS (ESI-TOF): calcd for C19H26O3SiNa (M + Na+)
353.1543, found 353.1536.
(S)-5h. Colorless oil, 71% yield (65.2 mg). The ee was determined
on a Daicel Chiralcel OD-H column with hexane/2-propanol = 85/15,
flow = 1.0 mL/min. Retention times: 11.1 min [major enantiomer],
16.3 min [minor enantiomer]. 90% ee. [α]25D = −3.7 (c 0.94, CHCl3).
1H NMR (CDCl3): δ 7.78 (d, 3JHH = 8.1 Hz, 1H), 7.70−7.66 (m, 2H),
3
Table 2, Entry 6 ((S)-3f). Colorless oil, 91% yield (73.1 mg, 3f/4f
7.45−7.35 (m, 6H), 7.35−7.30 (m, 2H), 7.10 (dd, JHH = 8.4 Hz and
> 99/1). [α]25 = +12.5 (c 1.13, CHCl3). The absolute configuration
2
3
4JHH= 1.8 Hz, 1H), 3.55 (ddd, JHH = 10.5 Hz and JHH= 7.6 and 4.5
D
was assigned by analogy with entry 1. 1H NMR (CDCl3): δ 7.40−7.33
(m, 3H), 7.32−7.27 (m, 2H), 7.11−7.04 (m, 2H), 7.03−6.96 (m, 2H),
2
3
Hz, 1H), 3.44 (ddd, JHH = 10.5 Hz and JHH= 7.8 and 6.9 Hz, 1H),
2.57 (dd, 3JHH = 12.4 and 3.5 Hz, 1H), 2.18−2.08 (m, 1H), 2.04 (dtd,
2JHH = 14.0 Hz and 3JHH = 7.8 and 3.5 Hz, 1H), 1.35 (bs, 1H), 0.28 (s,
3H), 0.22 (s, 3H). 13C NMR (CDCl3): δ 140.0, 137.2, 134.3, 133.8,
131.7, 129.3, 127.8, 127.71, 127.67, 127.3, 126.0, 125.7, 124.8, 62.2,
32.9, 32.3, −3.8, −5.2. HRMS (ESI-TOF): calcd for C21H24OSiNa (M
+ Na+) 343.1489, found 343.1495.
3
3
6.09 (ddd, JHH = 17.0, 10.1, and 9.1 Hz, 1H), 4.93 (ddd, JHH = 10.1
Hz, 2JHH = 1.7 Hz, and 4JHH = 0.9 Hz, 1H), 4.88 (ddd, 3JHH = 16.9 Hz,
2JHH = 1.7 Hz, and JHH = 1.1 Hz, 1H), 3.40 (d, JHH = 9.1 Hz, 1H),
2.10 (s, 3H), 0.32 (s, 3H), 0.26 (s, 3H). 13C NMR (CDCl3): δ 140.1,
138.6, 137.3, 135.0, 134.4, 130.6, 129.3, 127.6, 127.2, 125.9, 124.7,
113.1, 39.1, 20.3, −3.9, −4.8. HRMS (ESI-TOF): calcd for
C18H22SiNa (M + Na+) 289.1383, found 289.1387.
4
3
Table 2, Entry 9 ((S)-3i). Colorless oil, 78% yield (78.2 mg, 3i/4i
= 98/2). [α]20 = +42.2 (c 1.30, CHCl3). The absolute configuration
D
was assigned by analogy with entry 1. 1H NMR (CDCl3): δ 8.01−7.94
(S)-5f. Colorless oil, 66% yield (51.3 mg). The ee was determined
on two Daicel Chiralcel OD-H columns with hexane/2-propanol =
90/10, flow = 0.8 mL/min. Retention times: 25.5 min [major
enantiomer], 27.3 min [minor enantiomer]. 95% ee. [α]25D = −5.9 (c
(m, 1H), 7.84−7.77 (m, 1H), 7.63 (d, 3JHH = 8.2 Hz, 1H), 7.46−7.38
3
(m, 4H), 7.38−7.32 (m, 2H), 7.29 (t, JHH = 7.0 Hz, 2H), 7.15 (dd,
4
3
3JHH = 7.2 Hz and JHH = 1.0 Hz, 1H), 6.23 (ddd, JHH = 16.9, 10.1,
1
and 9.2 Hz, 1H), 4.99 (ddd, 3JHH = 10.1 Hz, 2JHH = 1.6 Hz, and 4JHH
=
1.20, CHCl3). H NMR (CDCl3): δ 7.40−7.34 (m, 3H), 7.33−7.29
3
0.8 Hz, 1H), 4.95 (ddd, 3JHH = 16.8 Hz, 2JHH = 1.6 Hz, and 4JHH = 1.1
Hz, 1H), 4.07 (d, 3JHH = 9.1 Hz, 1H), 0.26 (s, 3H), 0.24 (s, 3H). 13C
NMR (CDCl3): δ 138.5, 138.3, 137.1, 134.5, 134.2, 131.6, 129.3,
129.0, 127.7, 125.5, 125.44, 125.39, 125.37, 124.5, 123.7, 113.6, 38.0,
−3.5, −4.5. HRMS (ESI-TOF): calcd for C21H22SiNa (M + Na+)
325.1383, found 325.1386.
(m, 2H), 7.12−7.04 (m, 2H), 6.99 (t, JHH = 7.4 Hz, 1H), 6.95 (d,
3JHH = 7.9 Hz, 1H), 3.49 (dt, 2JHH = 10.4 Hz and 3JHH = 5.9 Hz, 1H),
3.36 (dt, 2JHH = 10.4 Hz and 3JHH = 7.3 Hz, 1H), 2.71−2.63 (m, 1H),
2.13 (s, 3H), 2.06−1.97 (m, 2H), 1.33 (bs, 1H), 0.31 (s, 3H), 0.17 (s,
3H). 13C NMR (CDCl3): δ 140.9, 137.7, 135.9, 134.2, 130.3, 129.2,
127.8, 126.5, 125.9, 124.5, 62.2, 33.4, 26.8, 20.6, −3.9, −5.2. HRMS
(ESI-TOF): calcd for C18H24OSiNa (M + Na+) 307.1489, found
307.1494.
(S)-5i. Colorless oil, 58% yield (43.0 mg). The ee was determined
on a Daicel Chiralcel OD-H column with hexane/2-propanol = 90/10,
flow = 1.0 mL/min. Retention times: 9.7 min [minor enantiomer],
14.5 min [major enantiomer]. 93% ee. [α]25D = +26.6 (c 1.11, CHCl3).
1H NMR (CDCl3): δ 8.10−8.03 (m, 1H), 7.86−7.79 (m, 1H), 7.63 (d,
3JHH = 8.2 Hz, 1H), 7.48−7.40 (m, 4H), 7.40−7.29 (m, 4H), 7.12 (d,
3JHH = 6.9 Hz, 1H), 3.54−3.45 (m, 1H), 3.43−3.33 (m, 2H), 2.22−
2.11 (m, 2H), 1.07 (t, 3JHH = 5.2 Hz, 1H), 0.23 (s, 3H), 0.10 (s, 3H).
13C NMR (CDCl3): δ 139.1, 137.5, 134.3, 134.1, 132.6, 129.3, 129.0,
127.8, 125.5, 125.44, 125.39, 125.3, 123.64, 123.59, 62.0, 33.4, 25.3,
−3.4, −5.2. HRMS (ESI-TOF): calcd for C21H24OSiNa (M + Na+)
343.1489, found 343.1484.
Table 2, Entry 7 ((S)-3g). Colorless oil, 83% yield (82.9 mg, 3g/4g
= 99/1). [α]25 = +32.8 (c 1.24, CHCl3). The absolute configuration
D
1
was assigned by analogy with entry 1. H NMR (CDCl3): δ 7.51 (dd,
3JHH = 7.9 Hz and JHH = 1.3 Hz, 1H), 7.44−7.40 (m, 2H), 7.38 (tt,
4
3JHH = 7.3 Hz and JHH = 1.6 Hz, 1H), 7.32 (t, JHH = 7.0 Hz, 2H),
4
3
3
4
7.16 (td, JHH = 7.5 Hz and JHH = 1.2 Hz, 1H), 6.98−6.92 (m, 2H),
3
3
5.99 (ddd, JHH = 16.9, 10.1, and 9.0 Hz, 1H), 4.96 (ddd, JHH = 10.1
Hz, 2JHH = 1.5 Hz, and 4JHH = 0.9 Hz, 1H), 4.90 (ddd, 3JHH = 17.0 Hz,
2JHH = 1.5 Hz, and JHH = 1.2 Hz, 1H), 3.87 (d, JHH = 9.1 Hz, 1H),
0.30 (s, 3H), 0.28 (s, 3H). 13C NMR (CDCl3): δ 141.4, 137.4, 136.6,
134.6, 133.1, 129.4, 128.6, 127.7, 127.2, 126.3, 124.4, 113.9, 42.3, −3.7,
−5.1. HRMS (ESI-TOF): calcd for C17H19BrSiNa (M + Na+)
353.0332, found 353.0330.
4
3
Table 2, Entry 10 ((S)-3j). Colorless oil, 94% yield (73.1 mg, 3j/4j
= 99/1). [α]25 = +31.5 (c 1.40, CHCl3). The absolute configuration
D
was assigned by analogy with entry 1. 1H NMR (CDCl3): δ 7.39−7.34
(m, 3H), 7.32 (t, 3JHH = 7.0 Hz, 2H), 7.17 (dd, 3JHH = 4.9 Hz and 4JHH
= 3.0 Hz, 1H), 6.69 (d, 3JHH = 5.0 Hz, 1H), 6.66−6.63 (m, 1H), 6.07−
5.98 (m, 1H), 4.98−4.93 (m, 1H), 4.91 (d, 3JHH = 17.0 Hz, 1H), 3.32
(S)-5g. Colorless oil, 72% yield (62.5 mg). The ee was determined
on a Daicel Chiralcel OD-H column with hexane/2-propanol = 95/5,
flow = 1.0 mL/min. Retention times: 10.4 min [major enantiomer],
5013
dx.doi.org/10.1021/jo400888b | J. Org. Chem. 2013, 78, 5007−5017