Samarium diiodide promoted tandem β-elimination and cross-pinacol coupling: A new access to 1-vinyl-1,2-diols with two adjacent quaternary carbon centers

Article abstract of DOI:10.1055/s-0032-1316588

A samarium diiodide promoted tandem β-elimination/cross-pinacol coupling was developed. A series of novel 1-vinyl-1,2-diols with two adjacent quaternary carbon centers were obtained in moderate to good yields. Possible reaction pathways are proposed. Georg Thieme Verlag Stuttgart New York.

Full text of DOI:10.1055/s-0032-1316588

PAPER
▌2763
paper
Samarium Diiodide Promoted Tandem β-Elimination and Cross-Pinacol
Coupling: A New Access to 1-Vinyl-1,2-diols with Two Adjacent Quaternary
Carbon Centers
Tandem β-Elimination/Cross-Pinacol Coupling
Yun-Hui Zhao,a Ru-Lin Ma,a Xing-Wen Sun,*a Guo-Qiang Lin*a,b
a
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, P. R. of China
Fax +86(21)55664460; E-mail: sunxingwen@fudan.edu.cn
b
Key Laboratory of Synthetic Chemistry of Natural Substances, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
345 Ling Ling Road, Shanghai 200032, P. R. of China
E-mail: lingq@mail.sioc.ac.cn
Received: 24.05.2012; Accepted after revision: 04.06.2012
pounds is more challenging and remain relatively
Abstract: A samarium diiodide promoted tandem β-elimina-
unexplored.5 Furthermore, for preparation of 1,2-diols
tion/cross-pinacol coupling was developed. A series of novel 1-vi-
with two adjacent quaternary carbon centers, however, far
nyl-1,2-diols with two adjacent quaternary carbon centers were
fewer reports have appeared in the literature because of
the inherent difficulties on quaternary carbon construc-
tion. In fact, efficient and straightforward access to asym-
metrical 1,2-diols with two adjacent quaternary carbon
centers remains a challenging topic in organic synthe-
sis.1m,4d,6
obtained in moderate to good yields. Possible reaction pathways are
proposed.
Key words: samarium diiodide, cross-pinacol coupling, 1,2-diol,
quaternary carbon center, tandem reaction
1,2-Diols are ubiquitous skeletons that can be found in a
wide range of natural products, biologically active mole-
cules as well as medicinally important agents, such as
macrolides, polyketides, carbohydrates, and alkaloids.1
Furthermore, certain 1,2-diol units are also used as effi-
cient building blocks in organic synthesis.2 Due to these
great importance, tremendous efforts have been devoted
to the development of methods for efficient synthesis of
1,2-diols. Among them, high efficient construction of 1,2-
diol units with broad structural diversity has attracted ma-
jor attention over the past two decades. For preparation of
1,2-diol units with quaternary carbon stereocenters, how-
ever, far fewer reports have appeared in the literature be-
cause the establishment of quaternary centers is among
the most restrictive in organic chemistry.3 The reductive
coupling reaction between two carbonyl compounds rep-
resents a valuable alternative to the osmium tetraoxide-
mediated dihydroxylation of alkenes for generating 1,2-
diols. Typically, SmI2-promoted pinacol couplings have
evolved significantly over the years to become one of the
most useful reactions for the stereoselective preparation
of 1,2-diols in acyclic and cyclic systems.1m,4 Samarium
diiodide can effectively promote the intermolecular re-
ductive dimerization of aldehydes or ketones, the so
called homocoupling of carbonyl compounds, giving rise
to C2-symmetrical diols. However, most of the reported
relevant pinacol cross-coupling reactions of two different
carbonyl compounds were focused on the SmI2-mediated
intramolecular pinacol couplings. The intermolecular pi-
nacol coupling reaction of two different carbonyl com-
In the past several years, we have been interested in sa-
marium diiodide mediated reactions for the synthesis of
diverse structurally important molecules.7 We have previ-
ously reported two new approaches for the preparation of
quaternary carbon-containing α-amino ketone derivatives
and 2-quaternary anti-1,3-diol units by SmI2-promoted re-
giospecific electrophilic amination of α-heterosubstituted
ketones and tandem aldol/Evans–Tishchenko reaction.7h,j
Concellón et al. showed that the reduction of α-halo-β-hy-
droxy esters and amides with SmI2 gives α,β-unsaturated
esters and amides with high stereochemical control.8 In-
spired by these results, we envisioned that α,β-elimination
of compound 5 might be carried out to give the corre-
sponding ketones 1 and 3. Compounds 1 and 3 subse-
quently underwent samarium-promoted ‘pseudo-
intramolecular’ pinacol coupling reaction to provide 1-vi-
nyl-1,2-diol units with two quaternary carbon centers
avoiding the homocoupling of ketones 1 or 3. Herein, we
wish to report our development of a new and efficient ap-
proach to 1-vinyl-1,2-diol units with two quaternary car-
bon centers via SmI2-promoted tandem elimination/cross-
pinacol coupling (Scheme 1). The 1-vinyl-1,2-diols can
be obtained in moderate to good yields with two adjacent
quaternary carbon centers.
Initially, we examined the tandem reaction of compound
5a (R1 = R2 = Me; R3 = R4 = Ph) in the presence of two
equivalents of SmI2 at room temperature to check the po-
tential of our hypothesis. To our delight, the reaction pro-
ceeded smoothly as we expected at room temperature in
THF; the desired 1,2-diol product 6a was indeed isolated
in 45% yield and confirmed by NMR spectra (Table 1, en-
try 1). When the substrate 5a was added to a solution of
freshly prepared SmI2 in THF via a syringe pump in 15
minutes, the same yield of 45% was obtained (entry 2).
SYNTHESIS 2012, 44, 2763–2769
Advanced online publication: 31.07.2012
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DOI: 10.1055/s-0032-1316588; Art ID: SS-2012-H0460-OP
© Georg Thieme Verlag Stuttgart · New York

2764
Y.-H. Zhao et al.
PAPER
The optimized experimental procedure for the SmI2-pro-
moted elimination/pinacol cross-coupling reaction is as
follows: Under nitrogen, a solution of freshly prepared
SmI2 in THF and the substrate 5a in freshly distilled THF
was reacted for 90 minutes. Subsequent workup and puri-
fication by column chromatography on silica gel gave 1-
vinyl-1,2-diol 6a in 83% yield (see experimental).
previous work: homo-pinacol coupling
HO
R1
R2
R2
R1
OH
O
O
SmI2
(1)
(2)
+
R1
R2
R2
R1
1
1
2
O
R3
R4
O
SmI2
Following the optimal reaction conditions, the scope of
the tandem elimination/pinacol cross-coupling procedure
was investigated and the results are summarized in Table
2. As shown in Table 2, the reaction sequence was found
very effective for a wide range of ketone substrates 5a–i.
In most cases, the tandem reaction product 1-vinyl-1,2-di-
ols were observed in moderate to good yields (Table 2, en-
tries 1–10). The reaction seems to be driven through
chelation of samarium to the in situ generated two differ-
ent ketones, which allow it to compete effectively with the
cross-pinacol coupling. We also explored the possibility
of using the ring heteroatom substituted substrates such as
compound 5k and 5l; the reactions took place with rela-
tively low yields, probably due to the chelation of samar-
ium with the ring heteroatom.
R4
R3
OH
R3
R4
3
4
this work: cross-pinacol coupling
O
1
R2
R1
HO R3
R3
O
SmI2
Sm3+
SmI2
R2
R1
OH
R4
O
R1 R2
O
R4
O
6
5
R4
R3
3
Scheme 1 Homo- and cross-pinacol couplings
Encouraged by these results, the influence of additive was
studied in this reaction. As shown in Table 1, when protic
solvent such as methanol, tert-butyl alcohol, or water was
added as the additive, the yield decreased dramatically
(entries 4–6). The addition of the most popularly em-
ployed Lewis base, HMPA, has no contribution to the
yield of product 6a (entry 7). Further optimization of the
reaction conditions indicated that a good yield of 83%
could be achieved by employing 4 equivalents of SmI2
(entry 8).
To better understand the reaction pathway as well as the
observed pinacol cross-coupling, we further conducted
some supporting experiments (Scheme 2).
As demonstrated in Scheme 2, the SmI2-promoted cross-
coupling reaction of chalcones and ketones gave much
lower yield compared with samarium diiodide promoted
tandem elimination/cross-pinacol coupling. For example,
SmI2-promoted tandem elimination/cross-pinacol cou-
pling of substrate 5j gave 1,2-diol compound 6j in 77%
yield, however, cross-coupling of chalcone 8 and cyclo-
hexanone only gave trace product 6j (Scheme 2, Equation
3). Based on the above results and according to the report
about β-elimination of O-acetylchlorohydrins promoted
by samarium diiodide,8 a possible mechanism was pro-
posed. The substrate 5a was eliminated to form chalcone
8 and acetone 9 in the presence of SmI2, then the cross-
coupling of these two different ketones taken placed al-
most simultaneously with the elimination of the substrate
(Scheme 3).
Table 1 Screening and Optimization of Reaction Conditionsa
Ph
O
Ph
OH
SmI2
O
THF, r.t., 1.5 h
OH
O
6a
5a
Entry
SmI2 (equiv)
Additive (equiv)
Yield (%)b
In conclusion, samarium diiodide-promoted tandem β-
elimination/cross-pinacol coupling has been developed.
To the best of our knowledge, this is the first example
about the pinacol cross-coupling of ketones with α,β-un-
saturated ketones. This methodology gave 1-vinyl-1,2-di-
ols with two adjacent quaternary carbon centers in
moderate to good yields.
1
2c
3
4
5
6
7
8
2
2
3
3
3
3
3
4
none
45
45
73
36
20
15
70
83
none
none
t-BuOH
MeOH
H2O
Melting points were measured on a Mel-Temp apparatus and are
uncorrected. 1H (400 MHz) and 13C (100 MHz) NMR spectra were
recorded on a Bruker AM-400 UltraShield, 400 MHz, high-perfor-
mance digital FT-NMR spectrometer with TMS as the internal and
external standards. FT-IR spectra were obtained with a Nicolet AV-
360 spectrophotometer. Low-resolution mass spectra (LRMS) and
high-resolution mass spectra (HRMS) were obtained on Finnigan
GC-MS 4021 and MAT-8430 instruments using the electron-
impact ionization technique (70 eV) or electrospray ionization.
HMPA
none
a All reactions were carried out with 0.3 mmol of compound 5a in 11
mL of THF at r.t.
b Isolated yield after chromatographic purification.
c The substrate 5a was added with a syringe in 15 min.
Synthesis 2012, 44, 2763–2769
© Georg Thieme Verlag Stuttgart · New York

PAPER
Tandem β-Elimination/Cross-Pinacol Coupling
2765
cross-coupling reaction
tandem reaction
O
O
O
SmI2 (4 equiv)
THF, r.t., 4 h
OH
(1)
+
OH
7
9
6a
41%
83%
O
OH
SmI2 (4 equiv)
THF, r.t., 4 h
OH
(2)
(3)
+
7
11
6h
55%
77%
O
O
OH
SmI2 (4 equiv)
THF, r.t., 4 h
OH
+
MeO
8
11
MeO
6j
trace
77%
O
O
OH
SmI2 (4 equiv)
THF, r.t., 4 h
(4)
OH
+
7
10
6i
51%
84%
Scheme 2 Pinacol cross-coupling reaction of ketones with α,β-unsaturated ketones
(E)-2-Methyl-3,5-diphenylpent-4-ene-2,3-diol (6a)
O
9
Yield: 67 mg (83%); white solid; mp 101–102 °C.
SmI2
O
Sm3+
O
IR (film): 3463, 3283, 3021, 2970, 2934, 1490, 1445, 1359, 1172,
1023, 968, 691 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.61 (d, J = 7.2 Hz, 2 H), 7.42 (d,
J = 7.6 Hz, 2 H), 7.36–7.21 (m, 6 H), 7.07 (d, J = 16.0 Hz, 1 H), 6.78
(d, J = 16.0 Hz, 1 H), 2.92 (s, 1 H), 2.07 (s,1 H), 1.31 (s, 3 H), 1.13
(s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 142.7, 136.9, 132.1, 130.9, 128.7,
127.9, 127.8, 127.3, 126.7, 80.8, 76.0, 25.5, 24.9.
HRMS (ESI): m/z [M + Na]+ calcd for C18H20O2Na+: 291.1361;
found: 291.1340.
β-elimination
O
O
Ph
5a
rate-determining step
Ph
Ph
8
samarium–ketone
complex
SmI2
cross-pinacol
coupling
HO Ph
OH
Ph
6a
Scheme 3 Possible mechanism for SmI2-promoted cross-pinacol cou-
pling
(E)-2-Methyl-5-phenyl-3-p-tolylpent-4-ene-2,3-diol (6b)
Yield: 60 mg (70%); white solid; mp 72–73 °C.
IR (film): 3455, 2977, 2924, 1506, 1485, 1448, 1372, 1342, 1165,
973, 815, 742, 693 cm–1.
1-Vinyl-1,2-diols by Tandem β-Elimination/Cross-Pinacol Cou-
pling; General Procedure
1H NMR (400 MHz, CDCl3): δ = 7.49 (d, J = 8.4 Hz, 2 H), 7.42 (d,
J = 8.8 Hz, 2 H), 7.06 (t, J = 7.2 Hz, 2 H), 7.25–7.21 (m, 1 H), 7.16
(d, J = 8.4 Hz, 2 H), 7.06 (d, J = 16.0 Hz, 1 H), 6.78 (d, J = 16.0 Hz,
1 H), 2.86 (s, 1 H), 2.33 (s, 3 H), 2.07 (s, 1 H), 1.30 (s, 3 H), 1.13 (s,
3 H).
13C NMR (100 MHz, CDCl3): δ = 139.7, 137.0, 136.9, 132.2, 130.7,
128.7, 128.6, 127.8, 127.2, 126.7, 80.8, 76.0, 25.4, 24.9, 21.1.
A solution of the appropriate substituted methanone 5 (0.3 mmol) in
THF (2 mL) was added to a stirred solution of SmI2 (1.2 mmol, 0.2
mol/L) at r.t. under a N2 atmosphere. After the time indicated in Ta-
ble 2, the reaction was quenched with sat. aq Na2S2O3 (2 mL) and
extracted with EtOAc (3 × 15 mL). The combined EtOAc layers
were washed with brine (20 mL), and dried (Na2SO4). The solution
was filtered and the filtrate was concentrated under reduced pres-
sure. The residue was purified by column flash chromatography
over silica gel (5:1 hexane–EtOAc) to provide the corresponding
pure product.
HRMS (ESI): m/z [M + Na]+ calcd for C19H22O2Na+: 305.1517;
found: 305.1484.
© Georg Thieme Verlag Stuttgart · New York
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Y.-H. Zhao et al.
PAPER
Table 2 SmI2-Promoted Tandem Elimination/Cross-Pinacol Couplinga
O
R3
R3
OH
R1
O
R2
R1
SmI2 (4 equiv)
THF, r.t.
R2
O
OH
R4
R4
5a–l
6a–l
Entry
R1, R2
R3
Ph
R4
Product
Time (h) Yield (%)b
1
2
Me
H
6a
1.5
1.5
83
70
OH OH
Me
Me
4-MeC6H4
H
H
6b
6c
OH OH
OMe
3
4
4-MeOC6H4
1.5
1.5
61
67
OH OH
F
Me
4-FC6H4
H
6d
OH OH
5
6
7
Me
Me
Me
Ph
Ph
Ph
Cl
6e
6f
3.0
3.0
2.5
69
53
78
OH OH
Cl
Br
OH OH
Br
MeO
6g
OH OH
MeO
Synthesis 2012, 44, 2763–2769
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PAPER
Tandem β-Elimination/Cross-Pinacol Coupling
2767
Table 2 SmI2-Promoted Tandem Elimination/Cross-Pinacol Couplinga (continued)
O
R3
R3
OH
R1
O
R2
R1
SmI2 (4 equiv)
THF, r.t.
R2
O
OH
R4
R4
5a–l
6a–l
Entry
R1, R2
(CH2)5
R3
Ph
R4
Product
Time (h) Yield (%)b
8
H
6h
5.0
77
OH
OH
Ph OH
HO
9
(CH2)4
(CH2)5
Ph
Ph
H
6i
6j
4.0
5.0
84
77
OH
Ph
10
MeO
HO
MeO
O
11
12
Me
Me
3-furyl
H
6k
1.5
3.0
35
21
OH OH
S
3-thienyl
H
6l
OH OH
a All reactions were carried out with 0.3 mmol of compound 5 in 11 mL of THF at r.t.
b Isolated yield after chromatographic purification.
(E)-3-(4-Methoxyphenyl)-2-methyl-5-phenylpent-4-ene-2,3-
diol (6c)
7.00 (m, 3 H), 6.76 (d, J = 16.0 Hz, 1 H), 2.94 (s, 1 H), 2.09 (s, 1 H),
1.29 (s, 3 H), 1.11 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 162.1 (d, J = 247.2 Hz), 138.5,
136.7, 131.5 (d, J = 55.2 Hz), 129.1, 129.0, 128.7, 128.4, 128.0,
126.7, 114.6 (d, J = 21.1 Hz), 80.6, 76.0, 55.3, 25.5, 24.8.
Yield: 55 mg (61%); white solid; mp 75–76 °C.
IR (film): 3453, 2980, 2934, 1609, 1509, 1454, 1301, 1250, 1178,
1034, 832, 732, 681 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.53 (d, J = 9.6 Hz, 2 H), 7.43 (d,
J = 6.8 Hz, 2 H), 7.32 (t, J = 7.6 Hz, 2 H), 7.26–7.23 (m, 1 H), 7.07
(d, J = 16.0 Hz, 1 H), 6.89 (d, J = 8.4 Hz, 2 H), 6.78 (d, J = 16.0 Hz,
1 H), 3.80 (s, 3 H), 2.83 (s, 1 H), 2.03 (s, 1 H), 1.30 (s, 3 H), 1.14 (s,
3 H).
13C NMR (100 MHz, CDCl3): δ = 158.7, 136.9, 134.8, 132.2, 130.7,
128.7, 128.4, 127.8, 126.7, 113.2, 80.6, 76.0, 55.3, 25.5, 24.8.
19F NMR (376 MHz, CDCl3): δ = –115.5 (s).
HRMS (ESI): m/z [M + Na]+ calcd for C18H19FO2Na+: 309.1267;
found: 309.1251.
(E)-5-(4-Chlorophenyl)-2-methyl-3-phenylpent-4-ene-2,3-diol
(6e)
Yield: 63 mg (69%); white solid; mp 100–101 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C19H22O3Na+: 321.1467;
found: 321.1451.
IR (film): 3484, 3303, 2978, 2929, 1588, 1509, 1490, 1446, 1359,
1171, 1091, 1022, 725, 706 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.61 (d, J = 7.2 Hz, 2 H), 7.37–
7.25 (m, 7 H), 7.05 (d, J = 16.0 Hz, 1 H), 6.74 (d, J = 16.0 Hz, 2 H),
2.96 (s, 1 H), 2.06 (s, 1 H), 1.31 (s, 3 H), 1.14 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 142.5, 135.4, 133.4, 132.7, 129.7,
128.8, 127.9, 127.4, 127.2, 80.7, 76.0, 25.4, 24.9.
HRMS (ESI): m/z [M + Na]+ calcd for C18H19ClO2Na+: 325.0971;
found: 325.0946.
(E)-3-(4-Fluorophenyl)-2-methyl-5-phenylpent-4-ene-2,3-diol
(6d)
Yield: 58 mg (67%); white solid; mp 71–72 °C.
IR (film): 3478, 2970, 2929, 1598, 1508, 1444, 1357, 1219, 1158,
1019, 835, 758, 691 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.58–7.55 (m, 2 H), 7.42 (d, J =
6.8 Hz, 2 H), 7.30 (t, J = 7.6 Hz, 2 H), 7.26–7.23 (m, 1 H), 7.04–
© Georg Thieme Verlag Stuttgart · New York
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Y.-H. Zhao et al.
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(E)-5-(4-Bromophenyl)-2-methyl-3-phenylpent-4-ene-2,3-diol
13C NMR (100 MHz, CDCl3): δ = 159.2, 142.9, 129.9, 129.8, 129.8,
127.9, 127.7, 127.5, 127.1, 114.1, 81.1, 76.7, 55.4, 32.0, 31.3, 25.6.
21.7, 21.7.
(6f)
Yield: 55 mg (53%); white solid; mp 98–99 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C22H26O3Na+: 361.1771;
found: 361.1780.
IR (film): 3468, 3283, 2976, 2934, 1486, 1446, 1358, 1172, 1069,
1022, 967, 765, 721 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 7.2 Hz, 2 H), 7.44 (d,
J = 9.2 Hz, 2 H), 7.35 (t, J = 7.2 Hz, 2 H), 7.30–7.25 (m, 3 H), 7.07
(d, J = 16.0 Hz, 1 H), 6.73 (d, J = 16.0 Hz, 1 H), 2.92 (s, 1 H), 2.01
(s, 1 H), 1.32 (s, 3 H), 1.13 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 142.5, 135.9, 132.9, 131.8, 129.7,
128.2, 127.9, 127.4, 127.2, 121.6, 80.8, 76.0, 25.4, 24.9.
(E)-3-(Furan-3-yl)-2-methyl-5-phenylpent-4-ene-2,3-diol (6k)
Yield: 27 mg (35%); white solid; mp 108–109 °C.
IR (film): 3447, 3298, 2980, 2924, 1603, 1498, 1444, 1359, 1165,
1038, 976, 947, 787, 691 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.47–7.46 (m, 1 H), 7.42–7.39 (m,
3 H), 7.34–7.30 (m, 2 H), 7.32 (t, J = 8.2 Hz, 2 H), 7.26–7.22 (m, 1
H), 6.82 (d, J = 16.0 Hz, 1 H), 6.69 (d, J = 16.0 Hz, 1 H), 6.50–6.49
(m, 1 H), 2.72 (s, 1 H), 2.12 (s, 1 H), 1.30 (s, 3 H), 1.22 (s, 3 H).
HRMS (ESI): m/z [M + Na]+ calcd for C18H19BrO2Na+: 369.0416;
found: 369.0466.
13C NMR (100 MHz, CDCl3): δ = 142.9, 140.5, 136.7, 130.8, 130.5,
128.7, 128.3, 127.9, 126.7, 110.3, 78.2, 75.6, 25.2, 25.0.
HRMS (ESI): m/z [M + Na]+ calcd for C16H18O3Na+: 281.1130;
found: 281.1154.
(E)-5-(4-Methoxyphenyl)-2-methyl-3-phenylpent-4-ene-2,3-
diol (6g)
Yield: 70 mg (78%); light yellow solid; mp 108–109 °C.
IR (film): 3466, 3303, 2970, 2924, 2832, 1640, 1607, 1572, 1511,
1445, 1246, 1168, 1021, 748, 712 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.62 (d, J = 7.2 Hz, 2 H), 7.36–
7.25 (m, 5 H), 6.95 (d, J = 16.0 Hz, 1 H), 6.86 (d, J = 8.8 Hz, 2 H),
6.73 (d, J = 16.0 Hz, 1 H), 3.80 (s, 3 H), 2.86 (s, 1 H), 2.08 (s, 1 H),
1.31 (s, 3 H), 1.13 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 159.4, 142.9, 130.5, 129.8, 129.7,
127.9, 127.8, 127.3, 127.2, 114.1, 80.8, 76.0, 55.4, 25.4, 24.8.
(E)-2-Methyl-5-phenyl-3-(thiophen-3-yl)pent-4-ene-2,3-diol
(6l)
Yield: 17 mg (21%); white solid; mp 102–103 °C.
IR (film): 3466, 3313, 2972, 2934, 1669, 1598, 1494, 1448, 1358,
1164, 1027, 971, 777, 691 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.43–7.41 (m, 2 H), 7.35–7.28 (m,
4 H), 7.26–7.24 (m, 1 H), 7.22–7.20 (m, 1 H), 6.89 (d, J = 16.0 Hz,
1 H), 6.79 (d, J = 16.0 Hz, 1 H), 2.92 (s, 1 H), 2.08 (s, 1 H), 1.31 (s,
3 H), 1.18 (s, 3 H).
HRMS (ESI): m/z [M + Na]+ calcd for C19H22O3Na+: 321.1467;
found: 321.1439.
13C NMR (100 MHz, CDCl3): δ = 144.4, 140.5, 136.8, 131.4, 130.4,
128.7, 127.9, 127.4, 125.2, 122.4, 80.5, 75.8, 25.4, 25.0.
(E)-1-(1-Hydroxy-1,3-diphenylallyl)cyclohexanol (6h)
Yield: 71 mg (77%); white solid; mp 134–135 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C16H18O2SNa+: 297.0890;
found: 297.0925.
IR (film): 3535, 3431, 2935, 2842, 1598, 1485, 1439, 1347, 1244,
1132, 1070, 965, 754, 698 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 7.2 Hz, 2 H), 7.43 (d,
J = 7.2 Hz, 2 H), 7.37–7.21 (m, 2 H), 7.26–7.23 (m, 6 H), 7.08 (d,
J = 16.0 Hz, 1 H), 6.81 (d, J = 16.0 Hz, 1 H), 2.92 (m, 1 H), 1.70–
1.48 (m, 9 H), 1.25–1.15 (m, 1 H), 1.03–0.95 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 142.7, 137.0, 132.1, 130.4, 128.7,
127.8, 127.7, 127.4, 127.2, 126.7, 81.0, 76.6, 32.0, 31.3, 25.6. 21.7.
Acknowledgment
Financial support from the National Natural Science Foundation of
China (21072031 and 20802009), and the Shanghai Municipal
Committee of Science and Technology (10ZR1404100) is grateful-
ly acknowledged.
HRMS (ESI): m/z [M + Na]+ calcd for C21H24O2Na+: 331.1662;
found: 331.1674.
Supporting Information for this article is available online at
(E)-1-(1-Hydroxy-1,3-diphenylallyl)cyclopentanol (6i)
Yield: 74 mg (84%); white solid; mp 110–111 °C.
http://www.thieme-connect.com/ejournals/toc/synthesis.SnoIufproi
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IR (film): 3544, 3382, 2945, 2868, 1593, 1490, 1446, 1378, 1150,
1085, 975, 876, 755, 698 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.65–7.62 (m, 2 H), 7.44–7.42 (m,
2 H), 7.37–7.21 (m, 2 H), 7.37–7.22 (m, 6 H), 7.03 (d, J = 16.0 Hz,
1 H), 6.85 (d, J = 16.0 Hz, 1 H), 2.99 (s, 1 H), 2.13–2.04 (m, 1 H),
1.87–1.72 (m, 3 H), 1.64 (s, 1 H), 1.58–1.47 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ = 143.2, 137.0, 132.3, 130.6, 128.7,
128.0, 127.8, 127.3, 127.2, 126.7, 87.9, 80.1, 35.7, 35.4, 24.0.
HRMS (ESI): m/z [M + Na]+ calcd for C20H22O2Na+: 317.1517;
found: 317.1522.
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© Georg Thieme Verlag Stuttgart · New York
Synthesis 2012, 44, 2763–2769