The Journal of Organic Chemistry
NOTE
8.5 Hz, 2H), 3.83 (s, 3H), 1.18 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
159.9, 138.1 (d, J = 7.1 Hz), 131.3 (d, J = 15.3 Hz), 131.0, 130.1, 129.6,
128.1, 127.3, 126.5, 125.2, 122.1, 114.4, 58.3, 55.4, 23.4; HRMS (ESI,
m/z) calcd for C19H22O2SNa [M + Na]+ 337.1238, found 337.1241.
(R,E)-1-(tert-Butylsulfinyl)-2-(4-fluorostyryl)benzene (6c): white so-
lid, 62% yield, mp 87À90 °C; [R]20D = 237.4 (c = 1.0, CHCl3); 1H NMR
(500 MHz, CDCl3) δ 7.91 (dd, J = 7.6, 1.5 Hz, 1H), 7.71À7.66 (m, 1H),
7.52À7.45 (m, 4H), 7.42 (d, J = 16.1 Hz, 1H), 7.08 (t, J = 8.6 Hz, 2H),
7.02 (d, J = 16.1 Hz, 1H), 1.18 (s, 9H); 13C NMR (125 MHz, CDCl3) δ
163.8, 161.9, 138.5, 137.8, 133.1, 131.3, 130.3, 128.4 (d, J = 8.0 Hz),
127.8, 126.7, 125.5, 124.2, 116.1, 115.9, 58.4, 23.4; 19F NMR (377 MHz,
CDCl3) δ À113.53 (s, 1F); HRMS (ESI, m/z) calcd for C18H19FOSNa
[M + Na]+ 325.1038, found 325.1044.
(R,E)-1-(tert-Butylsulfinyl)-2-(4-chlorostyryl)benzene (6d): white so-
lid, 60% yield, mp 113À116 °C; [R]20D = 220.5 (c = 1.0, CDCl3) 1H
NMR (400 MHz, acetone) δ 7.88 (dd, J = 10.2, 8.0 Hz, 2H), 7.67À7.62
(m, 3H), 7.61À7.52 (m, 2H), 7.44 (d, J = 8.5 Hz, 2H), 7.30 (d, J = 16.2
Hz, 1H), 1.14 (s, 9H); 13C NMR (100 MHz, acetone) δ 140.5, 138.4,
136.9, 134.3,132.1, 130.9, 129.9, 129.4, 128.7, 127.5, 126.4, 125.8, 58.5,
23.5; HRMS (ESI, m/z) calcd for C18H19ClOSNa [M + Na]+ 341.0743,
found 341.0737.
(R,E)-1-(tert-Butylsulfinyl)-2-(4-(trifluoromethyl)styryl)benzene (6e):
white solid, 61% yield, mp 77À79 °C; [R]20D = 183.9 (c = 1.0, CHCl3);
1H NMR (500 MHz, CDCl3) δ 7.97À7.91 (m, 1H), 7.75À7.70 (m, 1H),
7.68À7.57 (m, 5H), 7.51 (p, J = 7.3 Hz, 2H), 7.08 (d, J = 16.1 Hz, 1H),
1.18 (s, 9H); 13C NMR (125 MHz, CDCl3) δ 140.3 138.9 137.3 131.4
130.2, 129.9 (q, JC,F = 32.6 Hz), 128.3, 126.9, 125.9 (q, JC,F = 3.5 Hz),
125.7, 123.2, 58.5 23.4; 19F NMR (377 MHz, CDCl3) δ À63.15 (s, 3F);
HRMS (ESI, m/z) calcd for C19H19F3OSNa [M + Na]+ 375.1006, found
375.1009.
163.9 161.9 138.6, 137.8, 133.1, 131.3 130.3 128.4 (d, J = 8.1 Hz), 127.8,
126.8 125.5, 124.3 116.1, 115.9, 58.4, 23.5; 19F NMR (377 MHz,
CDCl3) δ À113.53 (s, 1F); HRMS (ESI, m/z) calcd for C18H19FOSNa
[M + Na]+ 325.1038, found 325.1039.
(S,E)-1-(4-Fluorostyryl)-2-(p-tolylsulfinyl)benzene (8b): following
the general procedure with (1S,2R,5S)-(+)-menthyl-(S)-p-Tol-sulfinate
in place of (R)-tert-butyl tert-butanethiosulfinate, white solid, 55% yield,
mp 82À85 °C; [R]20D = À115.9 (c = 1.0, CHCl3); 1H NMR (500 MHz,
CDCl3) δ 8.01À7.96 (m, 1H), 7.61 (dd, J = 5.9, 3.1 Hz, 1H), 7.51 (d, J =
8.2 Hz, 1H), 7.47À7.43 (m, 7H), 7.24 (d, J = 8.1 Hz, 1H), 7.18 (d, J = 8.1
Hz, 2H), 7.07 (t, J = 8.6 Hz, 2H), 6.94 (d, J = 16.1 Hz, 1H), 2.31 (s, 3H);
13C NMR (125 MHz, CDCl3) δ 163.9, 161.9, 143.1, 142.2,141.5,136.1,
132.9, 131.3 (d, J = 13.1 Hz), 130.1, 128.7, 128.5 (d, J = 8.1 Hz), 126.1,
125.4, 124.9 (d, J = 9.6 Hz), 123.0, 115.9 (d, J = 21.8 Hz), 21.5; 19F NMR
(377 MHz, CDCl3) δ À113.31 (s, 1F); HRMS (ESI, m/z) calcd for
C21H17FOSNa [M + Na]+ 359.0882, found 359.0890.
(R,E)-1-(2-(4-Fluorostyryl)phenylsulfinyl)-2-methoxynaphthalene
(8c): following the general procedure with (S)-L-menthyl 2-methoxy-
1-naphthalensulfinate47 in place of (R)-tert-butyl tert-butanethiosulfi-
nate, white solid, 50% yield, mp 95À97 °C; [R]20D = À162.2 (c = 0.6,
CHCl3); 1H NMR (500 MHz, CDCl3) δ 8.81 (dd, J = 8.7, 0.7 Hz, 1H),
8.36 (dd, J = 8.0, 1.2 Hz, 1H), 7.86 (d, J = 9.0 Hz, 1H), 7.74 (dd, J = 8.2,
0.5 Hz, 1H), 7.57À7.50 (m, 2H), 7.47 (d, J = 7.2 Hz, 1H), 7.42À7.36
(m, 2H), 7.07 (d, J = 9.1 Hz, 1H), 6.96À6.83 (m, 5H), 6.63 (d, J = 15.9
Hz, 1H), 3.71 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 163.4, 161.4,
157.6, 141.7, 135.1, 134.6, 132.8, 132.4, 130.1, 129.9, 129.2, 128.9,
128.5, 128.23, 127.3, 126.6, 125.6, 124.4, 123.7, 123.0, 122.6, 115.4,
115.3, 113.4, 56.5; 19F NMR (377 MHz, CDCl3) δ À114.09 (s, 1F);
HRMS (ESI, m/z) calcd for C25H19FO2SNa [M + Na]+ 425.0987,
found 425.0977.
(R,E)-1-(tert-Butylsulfinyl)-2-(3,3-dimethylbut-1-enyl)benzene (6f):
white solid, 57% yield, mp 47À50 °C; [R]20D = 138.1 (c = 1.1, CHCl3);
1H NMR (400 MHz, acetone) δ 7.81 (d, J = 9.1 Hz, 1H), 7.65 (d, J = 7.4
Hz, 1H), 7.53À7.43 (m, 2H), 6.77 (d, J = 16.0 Hz, 1H), 6.36 (d, J = 16.0
Hz, 1H), 1.14 (s, 9H), 1.13 (s, 9H); 13C NMR (100 MHz, acetone)
δ145.3 139.3 131.9, 127.8, 127.2 126.5 122.2 58.7, 34.5, 23.6; HRMS
(ESI, m/z) calcd for C16H24OSNa [M + Na]+ 287.1446, found
287.1448.
(S,E)-1-(4-Fluorostyryl)-2-(4-methoxyphenylsulfinyl)benzene (8d):
following the general procedure for the preparation with (S)-L-menthyl
p-methoxybenzenesulfinate48 instead of (R)-tert-butyl tert-butanethio-
sulfinate, white solid, 63% yield, mp 80À82 °C; [R]20D = À291.1 (c =
1
0.7, CHCl3); H NMR (500 MHz, CDCl3) δ 8.06À8.01 (m, 1H),
7.59À7.53 (m, 1H), 7.51À7.40 (m, 6H), 7.37 (d, J = 16.0 Hz, 1H),
7.10À7.04 (m, 2H), 6.91 (d, J = 16.0 Hz, 1H), 6.89À6.85 (m, 2H), 3.76
(s, 3H); 13C NMR (125 MHz, CDCl3) δ 163.8, 161.8, 142.9, 136.3,
135.7, 132.9, 131.2, 131.0, 128.6, 128.36 (d, J = 8.1 Hz), 127.48 (s),
126.1, 124.5, 122.8, 115.9, 115.8, 114.76, 55.5; 19F NMR (377 MHz,
CDCl3) δ À113.38 (s, 1F); HRMS (ESI, m/z) calcd for C21H17FO2SNa
[M + Na]+ 375.0831, found 375.0839.
Asymmetric 1,4-Addition of Arylboronic Acids to Enones.
Under nitrogen atmosphere, a mixture of [RhCl(C2H4)2]2 (1.2 mg,
0.003 mmol) and 6c (2.0 mg, 0.0066 mmol) in 1 mL toluene was stirred
at room temperature for 1 h, at which time arylboronic acid (0.45 mmol)
was added, followed by enone (0.30 mmol), aqueous KOH (0.75 M in
H2O, 0.20 mL, 0.15 mmol), and toluene (1 mL). The reaction was
stirred at 40 °C and monitored by TLC. When the reaction was over, the
reaction mixture was concentrated in vacuo and purified by silica gel
flash column chromatography to afford the product.
(R,Z)-4-(2-(tert-Butylsulfinyl)styryl)-1,2-dimethoxybenzene (7a):
light yellow oil, 82% yield; [R]20 = 124.2 (c = 2.0, CHCl3); 1H
D
NMR (400 MHz, acetone) δ 7.85 (d, J = 7.8 Hz, 2H), 7.58À7.49 (m,
2H), 7.46 (d, J = 16.0 Hz, 1H), 7.22 (dd, J = 9.0, 7.0 Hz, 2H), 7.17 (dd,
J = 8.3, 1.8 Hz, 1H), 6.98 (d, J = 8.3 Hz, 1H), 3.88 (s, 3H), 3.84 (s, 3H),
1.14 (s, 9H); 13C NMR (100 MHz, acetone) δ 151.1 150.7, 139.9,
139.1132.3 132.0, 131.1 127.9, 127.3, 126.1 122.8, 121.1 112.9, 111.1
56.3 30.6 23.6; HRMS (ESI, m/z) calcd for C20H24O3SNa [M + Na]+
367.1344, found 367.1344.
(R,Z)-2-(2-(tert-Butylsulfinyl)styryl)-1,3,5-trimethoxybenzene (7b):
light yellow solid, 89% yield, mp 110À113 °C; [R]20 = 224.7 (c =
D
1.1, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.93 (d, J = 16.4 Hz, 1H),
7.87 (d, J = 7.8 Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.45 (t, J = 7.5 Hz, 1H),
7.40 (d, J = 9.7 Hz, 1H), 7.36 (d, J = 8.1 Hz, 1H), 6.16 (s, 2H), 3.89 (s,
6H), 3.83 (s, 3H), 1.20 (s, 9H); 13C NMR (100 MHz, CDCl3) δ
61.26,158.6 139.7 138.1 130.9, 129.8127.5, 126.9, 126.6 126.0 (t, J = 18.7
Hz), 125.3, 124.7 123.2 122.1, 107.4 90.9 90.6 58.3 55.9, 55.4, 55.3, 23.5;
HRMS (ESI, m/z) calcd for C21H26O4SNa [M + Na]+ 397.1450, found
397.1437.
3-Phenylcyclohexanone (13aa) (ref 16): colorless oil, 94% yield,
92% ee, [R]20 = À12.6 (c = 1.0, CHCl3); Chiracel AD-H column,
D
210 nm, n-hexane/i-propanol = 97/3, flow = 0.8 mL/min, tR = 9.9 and
11.8 min; 1H NMR (500 MHz, CDCl3) δ 7.39À7.28 (m, 2H),
7.26À7.19 (m, 3H), 3.01 (tt, J = 11.8, 3.9 Hz, 1H), 2.62À2.34 (m,
4H), 2.18À2.05 (m, 2H), 1.90À1.72 (m, 2H); 13C NMR (125 MHz,
CDCl3) δ 211.1, 144.5, 128.8, 126.7, 49.0, 44.9, 41.3, 32.9, 25.6.
3-(2-Methoxyphenyl)cyclohexanone (13ab) (ref 16): colorless oil,
(S,E)-1-(tert-Butylsulfinyl)-2-(4-fluorostyryl)benzene (8a): following
the general procedure with (S)-tert-butyl tert-butanethiosulfinate in
place of (R)-tert-butyl tert-butanethiosulfinate, gray-white solid, 63%
yield, mp 66À68 °C; [R]20D = À199.7 (c = 0.8, CHCl3); 1H NMR (500
MHz, CDCl3) δ 7.92 (dd, J = 7.3, 1.9 Hz, 1H), 7.68 (dd, J = 7.5, 1.5 Hz,
1H), 7.50À7.45 (m, 4H), 7.43 (d, J = 16.1 Hz, 1H), 7.13À7.06 (m, 2H),
7.02 (d, J = 16.1 Hz, 1H), 1.18 (s, 9H); 13C NMR (125 MHz, CDCl3) δ
91% yield, 95% ee, [R]20 = À31.3 (c = 1.0, CHCl3); Chiracel OJ-H
D
column, 210 nm, n-hexane/i-propanol = 98/2, flow = 1.0 mL/min, tR =
13.4 and 14.3 min; 1H NMR (400 MHz, CDCl3) δ 7.28À7.13 (m, 2H),
6.94 (t, J = 7.4 Hz, 1H), 6.87 (d, J = 8.1 Hz, 1H), 3.81 (s, 3H), 3.49À3.36
(m, 1H), 2.65À2.31 (m, 4H), 2.20À1.97 (m, 2H), 1.92À1.73 (m, 2H);
7260
dx.doi.org/10.1021/jo2011472 |J. Org. Chem. 2011, 76, 7256–7262