22 Arisawa, Toriyama, and Yamaguchi
3057, 2958, 2920, 1722, 1493, 1444, 1155, 1130, 756,
2.8 Hz, 1H), 2.07–2.12 (m, 1H), 2.18 (dt, J = 14.1, 3.1
Hz, 1H), 2.47 (ddd, J = 16.1, 4.4, 2.8 Hz, 1H), 3.27
(ddd, J = 16.4, 14.1, 6.1 Hz, 1H), 7.25 (t, J = 7.4 Hz,
1H), 7.36 (t, J = 7.9 Hz, 2H), 7.48 (d, J = 7.6 Hz,
2H). 13C NMR (100 MHz, CDCl3) δ: 12.8, 26.8, 27.3,
32.1, 37.2, 42.2, 44.6, 62.7, 126.9, 128.3, 128.5, 140.4,
203.4. IR (KBr): 3059, 2955, 2862, 1701, 1495, 1442,
1411, 1365, 1234, 1139, 749, 700, 555 cm−1. MS (EI)
m/z: 276 (M+, 29%), 230 (M+ – CH2S, 100%), 219 (M+
– C4H9, 93%). HRMS Calcd for C17H24OS: 276.1548.
Found: 276.1562. NOESY was observed between the
axial 6-proton (δ 3.27) and SMe protons (δ 1.73). cis-
8: Colorless oil. 1H NMR (600 MHz, CDCl3) δ: 0.94 (s,
9H), 1.56 (qd, J = 12.4, 4.7 Hz, 1H), 1.63 (tt, J = 12.1,
2.8 Hz, 1H), 1.82 (s, 3H), 1.90 (dd, J = 13.9, 12.2 Hz,
1H), 1.95–2.00 (m, 1H), 2.44 (td, J = 13.3, 6.3 Hz,
1H), 2.52 (ddd, J = 14.0, 4.4, 3.4 Hz, 1H), 2.91 (dt, J
= 14.0, 3.0 Hz, 1H), 7.22 (d, J = 7.6 Hz, 2H), 7.28 (t,
J = 7.6 Hz, 1H), 7.38 (t, J = 7.9 Hz, 2H). 13C NMR
(100 MHz, CDCl3) δ: 12.5, 27.4, 28.4, 32.6, 38.5, 39.3,
42.8, 63.4, 127.2, 127.4, 128.8, 138.3, 208.9. IR (neat):
3059, 2960, 2870, 1714, 1446, 1367, 1230, 1142, 744,
700, 565 cm−1. MS (EI) m/z: 276 (M+, 32%), 230
(M+ – CH2S, 100%), 219 (M+ – C4H9, 79%). HRMS
Calcd for C17H24OS: 276.1548. Found: 276.1540.
NOESY was observed between the axial 4-proton (δ
1.63) and Ph ortho-protons (δ 7.22), and between
the axial 6-proton (δ 2.44) and Ph ortho-protons
(δ 7.22).
700 cm−1. MS (EI) m/z: 206 (M+, 48%), 163 (M+
–
C3H7, 88%), 160 (M+ – CH2S, 100%). HRMS Calcd
for C12H14OS: 206.0765. Found: 206.0755.
2-Methylthio-2-phenylcyclohexanone
1
Colorless oil. H NMR (400 MHz, CDCl3) δ: 1.68–
1.78 (m, 1H), 1.77 (s, 3H), 1.86–2.00 (m, 3H), 2.13–
2.20 (m, 1H), 2.40–2.54 (m, 2H), 2.92 (ddd, J = 14.7,
9.1, 5.5 Hz, 1H), 7.24–7.28 (m, 1H), 7.34–7.38 (m,
4H). 13C NMR (100 MHz, CDCl3) δ: 12.5, 21.8, 26.7,
38.6, 40.4, 63.6, 127.2, 127.9, 128.5, 139.1, 205.8. IR
(neat): 3058, 2939, 2863, 1714, 1697, 1493, 1446,
1121, 747, 700 cm−1. MS (EI) m/z: 220 (M+, 29%),
177 (M+ – C3H7, 26%), 174 (M+ – CH2S, 99%), 145
(M+ – MeSC2H4, 100%). HRMS Calcd for C13H16OS:
220.0922. Found: 220.0914.
2-Methylthio-2-phenylcycloheptanone
Synthesized from 2-phenylcycloheptanone [9,11].
Colorless oil. 1H NMR (400 MHz, CDCl3) δ: 1.36–1.73
(m, 4H), 1.69 (s, 3H), 1.79–1.86 (m, 1H), 1.96–2.14
(m, 3H), 2.54 (dd, J = 11.0, 8.2 Hz, 1H), 3.07 (td, J =
11.7, 2.1 Hz, 1H), 7.25 (t, J = 6.8 Hz, 1H), 7.35 (t, J =
7.6 Hz, 2H), 7.46 (d, J = 8.0 Hz, 2H). 13C NMR (100
MHz, CDCl3) δ: 13.3, 24.3, 25.7, 30.1, 39.4, 40.4, 64.4,
126.9, 128.1, 129.2, 138.5, 203.5. IR (neat): 2929,
2856, 1685, 1493, 1456, 1444, 1157, 941, 752, 702
cm−1. MS (EI) m/z: 234 (M+, 100%), 191 (M+– C3H7,
88%), 163 (M+ – C5H11, 50%), 159 (M+ – MeSC2H4,
77%). HRMS Calcd for C14H18OS: 234.1078. Found:
234.1081.
δ1.56 H
δ1.90
δ2.47
H
O
H
δ0.88
2.10
δ
H
δ7.25
(2S∗,4S∗)- and (2R∗,4S∗)-4-(t-Butyl)-2-methyl-
thio-2-phenylcyclohexanone Trans-8 and Cis-8
H
H
δ7.36
δ7.48
δ2.18
3.27S
δ
In
a
two-necked flask equipped with
a
re-
2.02
δ
H
flux condenser, RhH(PPh3)4 (4 mol%, 11.5 mg),
dppe (8 mol%, 8.0 mg), (2R∗,4S∗)-4-(t-butyl)-2-
phenylcyclohexanone cis-7 [12] (1.25 mmol, 287.9
mg), 1 (0.25 mmol, 47.8 mg), and 3 (12 mol%, 2.7
L) in THF (0.25 mL) under an argon atmosphere
were placed, and the solution was heated at 90◦C
for 9 h. The solvent was removed under reduced
pressure, and the residue was purified by flash col-
umn chromatography on silica gel giving trans-8
(22.2 mg, 32%), cis-8 (14.4 mg, 21%), 6 (3.7 mg,
6%), 5 (24.8 mg, 68%) as well as the recovery of cis-7
(214.3 mg, 74%), trans-7 (43.2 mg, 15%), and 1 (8.5
mg, 18%). trans-8: Colorless crystals. mp 99–100◦C
(hexane). 1H NMR (600 MHz, CDCl3) δ: 0.88 (s, 9H),
1.56 (tdd, J = 13.5, 12.0, 4.5 Hz, 1H), 1.73 (s, 3H),
1.90 (dd, J = 14.1, 12.7 Hz, 1H), 2.02 (tt, J = 12.3,
H3C
NOESY
δ1.73
trans-8
δ1.56 H
δ2.52
δ1.90
O
H
H
δ1.97
δ0.94
δ1.82
H
SMe
H
H
δ2.91
2.44
δ
δ1.63
H
H
Hδ7.22
H δ7.38
NOESY
H
δ7.28
H
cis-8
Heteroatom Chemistry DOI 10.1002/hc