CuI-catalyzed tandem carbomagnesiation/carbonyl addition of Grignard reagents with acetylenic ketones: Convenient access to tetrasubstituted allylic alcohols

Article abstract of DOI:10.1016/j.jorganchem.2011.07.031

Highly functionalized tetrasubstituted allylic alcohols were prepared conveniently by CuI-catalyzed tandem carbomagnesiation/carbonyl addition of Grignard reagents with acetylenic ketones. The obtained allylic alcohols can be further transformed to polysu

Full text of DOI:10.1016/j.jorganchem.2011.07.031

Journal of Organometallic Chemistry 696 (2011) 3397e3401
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
CuI-catalyzed tandem carbomagnesiation/carbonyl addition of Grignard reagents
with acetylenic ketones: Convenient access to tetrasubstituted allylic alcohols
*
Meihua Xie , Chengyou Feng, Jitan Zhang, Changqing Liu, Kuang Fang, Guanying Shu, Wansheng Zuo
Key Laboratory of Functional Molecular Solids (Ministry of Education), Anhui Key Laboratory of Molecular Based Materials, College of Chemistry and Materials Science,
Anhui Normal University, Wuhu 241000, China
a r t i c l e i n f o
a b s t r a c t
Article history:
Highly functionalized tetrasubstituted allylic alcohols were prepared conveniently by CuI-catalyzed
tandem carbomagnesiation/carbonyl addition of Grignard reagents with acetylenic ketones. The
obtained allylic alcohols can be further transformed to polysubstituted indenes by intramolecular
cyclization.
Received 17 June 2011
Received in revised form
20 July 2011
Accepted 22 July 2011
Ó 2011 Elsevier B.V. All rights reserved.
Keywords:
Allylic alcohol
Acetylenic ketone
Grignard reagent
CuI
Indene
1. Introduction
reaction with electrophiles is a typical and time-tested method for
the formation of polysubstituted alkenes and has been extensively
Allylic alcohols are important structural motifs in many natural
products and bioactive compounds [1e4]. Allylic alcohols are also
valuable intermediates in many synthetic applications. For
example, allylic alcohols are potential precursors to allylic amines
[5e7], epoxy alcohols [8], cyclopropyl alcohols [9,10], and natural
products [11e14]. Therefore, development of new methods to
synthesize allylic alcohols is in high demand. Addition of alke-
nylmetal reagents to carbonyl compounds and the reductive
coupling of alkynes and carbonyl compounds are the commonly
used methods to synthesize allylic alcohols and substantial prog-
ress has been made in the synthesis of di- or trisubstituted allylic
alcohols by these methods [15e20]. In sharp contrast, few general
methods exist that allow the direct creation of tetrasubstituted
allylic alcohols [21e23].
Multicomponent tandem reaction allows formation of several
bonds in a single manipulation and it offers rapid and convergent
construction of complex structures from readily available materials.
Tandem reaction has become a powerful and useful tool in organic
synthesis and has remained an active area of research for organic
chemists [24e29]. Carbometalation of alkynes and its further
studied [30e35]. However, synthesis of tetrasubstituted allylic
alcohols by tandem carbometalation of alkynes and coupling with
carbonyl compounds are relatively scarce [21e23]. Furthermore, to
the best of our knowledge, synthesis of allylic alcohols by carbo-
magnesiation reaction of Grignard reagents and
a,b-acetylenic
ketones has not been reported so far. In continuation of our
research interest in exploring carbometalation of alkynes and its
application in the synthesis of polysubstituted alkenes [23,36e38],
we investigated the reaction of Grignard reagents with acetylenic
ketones, hoping to synthesize carbonyl-contained polysubstituted
alkenes. The results show that tandem carbomagnesiation/carbonyl
addition was happened and highly functionalized tetrasubstituted
allylic alcohols containing cabonecarbon triple bond and carbonyl
group were obtained in good yields in a single operation. Herein,
we wish to report the novel one-pot synthesis of highly function-
alized tetrasubstituted allylic alcohols via the CuI-catalyzed tandem
carbomagnesiation/carbonyl addition of Grignard reagents with
acetylenic ketones.
2. Results and discussion
Initially, the reaction of phenylmagnesium bromide with 1,3-
diphenyl-2-propyn-1-one (1a) was examined. It was found that
a complex mixture of products was obtained when 1.2 equiv
* Corresponding author. Tel.: þ86 553 3869310; fax: þ86 0553 3883517.
E-mail address: xiemh@mail.ahnu.edu.cn (M. Xie).
0022-328X/$ e see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2011.07.031

3398
M. Xie et al. / Journal of Organometallic Chemistry 696 (2011) 3397e3401
Table 2
PhMgBr react with 1a in THF in the presence of 10 mol% CuI
at ꢀ20 ꢁC. Fortunately, product 3a was obtained in 61% yield when
0.5 equiv PhMgBr was used (Table 1, entry 1). Product 3a was
obtained in a similar yield when THF was replaced by Et2O or
toluene/THF (Table 1, entries 2 and 3). The yield of 3a was improved
to 90% when the reaction was carried out in THF/CH2Cl2 (v/v 1/1)
(Table 1, entry 4). The amount of compound 3a was greatly
decreased in the elevated temperature (Table 1, entries 5 and 6).
Other Cu-catalyst such as CuCN or Cu(OTf)2 is less effective than CuI
(Table 1, entries 7 and 8). An increase in the amount of CuI has no
apparent effect on the reaction while the yield of 3a was decreased
when the amount of CuI reduced from 10 mol% to 5 mol% (Table 1,
entries 10 and 11). Thus, we defined 10 mol% CuI, 0.5 equiv of
Grignard reagent, 1.0 equiv actylenic ketone and THF/CH2Cl2 as
solvent at ꢀ20 ꢁC as the standard reaction conditions.
Tandem carbomagnesiation/carbonyl addition of Grignard reagents and acetylenic
ketones.
O
C
R1
R1
R2
R2
O
CuI (10 mol%)
R1MgBr
R1
C R2
R1
+
THF/CH2Cl2
-20
HO
1
2
3
Entry
R1
R2
Yield (%)a
1
2
3
4
5
6
7
8
9
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
90 (3a)
92 (3b)
93 (3c)
65 (3d)
70 (3e)
60 (3f)
62 (3g)
60 (3h)
61 (3i)
56 (3j)
4-CH3OC6H4
2,4-(CH3O)2C6H3
4-ClC6H4
4-O2NC6H4
n-C3H7
Under the optimized reaction conditions, we next examined the
scope of the reaction. It was found that the tandem carbomagne-
siation/carbonyl addition of Grignard reagents and acetylenic
ketones proceeded smoothly and differently substituted allylic
alcohols were obtained in good to excellent yields. The results are
compiled in Table 2. Grignard reagents can be phenylmagnesium
bromide or n-butylmagnesium bromide. R1 in acetylenic ketones
can be phenyl or n-butyl and R2 in acetylenic ketones can be phenyl
(Table 2, entries 1 and 8), electron-rich phenyl (Table 2, entries 2, 3
and 9), electron-deficient phenyl (Table 2, entries 4, 5 and 10), n-
propyl (Table 2, entry 6) and 2-furyl (Table 2, entry 7). Unfortu-
nately, a mixture of (Z)- and (E)-isomers was obtained when R1 in
acetylenic ketone is different from the R in RMgBr.
2-furyl
Ph
4-CH3OC6H4
4-ClC6H4
n-C4H9
n-C4H9
n-C4H9
10
a
Isolated yield based on 1.
were synthesized conveniently by tandem carbomagnesiation/
carbonyl addition of Grignard reagents and acetylenic ketones. The
obtained tetrasubstituted allylic alcohols can be conveniently
converted to polysubstituted indenes. Further studies and appli-
cations of the tandem reaction are ongoing in our laboratory.
3. Experimental
The molecular structure of compound 3a was determined by X-
ray diffraction analysis (Fig 1) [39].
All solid products were recrystallized from ethyl acetate and
hexane, and the melting points are uncorrected. All reactions were
carried out under an argon atmosphere. THF was distilled from
sodium-benzophenone and CH2Cl2 was distilled from calcium
hydride before use. 1H NMR spectra were measured at 300 MHz
and 13C NMR spectra were measured at 75 MHz in CDCl3 with TMS
as the internal standard. Acetylenic ketones were prepared
according to the previously described procedures [46,47].
Carbonyl, hydroxyl and carbonecarbon triple bond are useful
functional groups in organic transformations, so it is predictable
that the highly functionalized compounds 3 are potential inter-
mediates in organic synthesis. Substituted indenes are important
building blocks for many functional materials, medicines and
metallocene-based catalysts [40e44]. The utility of compound 3 as
useful synthetic intermediates was investigated by FeCl3$6H2O-
catalyzed intramolecular cyclization, which afforded functionalized
indenes in good to excellent yields (Scheme 1). The molecular
structure of compound 4c was affirmatively characterized by X-ray
diffraction analysis (Fig. 2) [45].
3.1. General procedure for the synthesis of allylic alcohols 3
RMgBr (0.5 mmol) and CuI (20 mg, 0.1 mmol) in THF (2 mL)
were added dropwise to the solution of acetylenic ketone
(1.0 mmol) in CH2Cl2 (2 mL) at ꢀ20 ꢁC. The reaction mixture was
stirred at ꢀ20 ꢁC for 5e10 min. After acetylenic ketone was
completely consumed (monitored by TLC), the reaction was
quenched with saturated NH4Cl and extracted with ethyl acetate.
The organic phase was combined and dried over anhydrous Na2SO4.
After filtration and removal of solvent in vacuo, the crude product
In summary, highly functionalized tetrasubstituted allylic alco-
hols containing cabonecarbon triple bond and carbonyl group
Table 1
Optimization of reaction conditions
O
PhMgBr (2a)
(0.5 equiv.)
catalyst
O
C Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a
OH
1a
.
Entry
Catalyst (10 mol%)
Temperature (ꢁC)
Solvent
Yield (%)a
1
2
3
4
5
6
7
8
CuI
CuI
CuI
CuI
CuI
CuI
CuCN
Cu(OTf)2
CuI
ꢀ20
ꢀ20
ꢀ20
ꢀ20
25
reflux
ꢀ20
ꢀ20
ꢀ20
ꢀ20
THF
Et2O
61
55
68
90
64
10
85
80
88
60
Toluene/THF
THF/CH2Cl2
THF/CH2Cl2
THF/CH2Cl2
THF/CH2Cl2
THF/CH2Cl2
THF/CH2Cl2
THF/CH2Cl2
10b
11c
CuI
a
Isolated yield based on 1a.
20 mol% CuI was used.
5 mol% CuI was used.
b
c
Fig. 1. The molecular structure of compound 3a.

M. Xie et al. / Journal of Organometallic Chemistry 696 (2011) 3397e3401
3399
125.7, 124.3, 121.5, 118.5, 110.2, 109.4, 109.3, 108.9, 90.1, 86.9, 72.5,
55.0, 54.8, 54.6; HRMS (EI) calcd. for C40H34O6, 610.2355, found,
O
Ph
6 H2O
FeCl3
C R2
O
Ph
Ph
(5 mol%)
610.2359; IR (KBr) 3493, 3057, 2933, 2160, 1658, 1595 cmꢀ1
.
C R2
CH2Cl2, -20 oC
Ph
HO R2
R2
3.1.4. 1,3-Bis(4-chlorophenyl)-2-(diphenylmethylene)-3-hydroxy-
Ph
3
4
5-phenylpent-4-yn-1-one (3d)
White solid; m.p. 146e147 ꢁC; 1H NMR (300 MHz, CDCl3)
d 7.99
R2: Ph (4a), 74%; 4-CH3OPh (4b), 67%;
4-ClPh (4c), 96%; n-C3H7 (4d), 55%
(d, J ¼ 8.0 Hz, 2H), 7.48 (d, J ¼ 8.1 Hz, 2H), 7.45e7.38 (m, 5H),
7.33e7.30 (m, 2H), 7.15e6.94 (m, 12H), 3.41 (s, 1H); 13C NMR
(75 MHz, CDCl3) d 197.0, 145.3, 142.6, 141.9, 140.4, 139.5, 139.1, 136.1,
Scheme 1. Synthesis of indenes 4 from compounds 3.
133.7, 131.6, 131.0, 129.1, 129.0, 128.9, 128.6, 128.5, 128.4, 128.1,
128.0, 127.9, 127.6, 127.1, 122.0, 90.4, 88.7, 73.2; HRMS (EI) calcd. for
C36H24Cl2O2
(
35Cl), 558.1153, found, 558.1148; IR (KBr) 3466, 3057,
was purified by flash chromatography (silica/hexaneeethyl acetate
10:1 v/v). The desired products 3 were obtained.
2229, 1666, 1583 cmꢀ1
.
3.1.5. 2-(Diphenylmethylene)-3-hydroxy-1,3-bis(4-nitrophenyl)-5-
phenylpent-4-yn-1-one (3e)
3.1.1. 2-(Diphenylmethylene)-3-hydroxy-1,3,5-triphenylpent-4-yn-
1-one (3a)
Yellow solid; m.p. 96e97 ꢁC; 1H NMR (300 MHz, CDCl3)
White solid; m.p. 118e120 ꢁC; 1H NMR (300 MHz, CDCl3)
d
8.08
(d, J ¼ 7.1 Hz, 2H), 7.61 (s, 2H), 7.37e7.34 (m, 8H), 7.19 (s, 3H),
7.09e6.98 (m, 10H), 3.41 (s, 1H); 13C NMR (75 MHz, CDCl3):
198.3,
d
8.25e8.10 (m, 4H), 8.02 (d, J ¼ 8.0 Hz, 2H), 7.72 (d, J ¼ 8.4 Hz, 2H),
7.40 (s, 5H), 7.15e6.97 (m, 10H), 3.68 (s, 1H); 13C NMR (75 MHz,
CDCl3) 196.4, 150.2, 149.8, 147.2, 147.0, 142.3, 140.8, 139.8, 138.4,
d
d
144.6, 144.1,142.5, 140.8, 139.3, 137.7, 132.9, 131.5, 129.7,129.1, 129.0,
128.7,128.3, 128.1, 127.9,127.8, 127.7, 127.5,127.4, 126.9, 126.8, 122.4,
90.8, 88.3, 73.7; HRMS (EI) calcd. for C36H26O2, 490.1933, found,
131.4, 130.1, 129.4, 129.2, 128.8, 128.6, 128.4, 128.2, 127.8, 127.7,
127.6, 123.4, 122.9, 121.2, 89.8, 89.3, 73.0; HRMS (EI) calcd. for
C36H24N2O6, 580.1634, found, 580.1638; IR (KBr) 3489, 3055, 2223,
490.1931; IR (KBr) 3518, 3062, 2222, 1597 cmꢀ1
.
1676, 1602, 1517, 1346 cmꢀ1
.
3.1.2. 2-(Diphenylmethylene)-3-hydroxy-1,3-bis(4-methoxyphenyl)-
3.1.6. 5-(Diphenylmethylene)-6-hydroxy-6-(2-phenylethynyl)
5-phenylpent-4-yn-1-one (3b)
White solid; m.p. 149e150 ꢁC; 1H NMR (300 MHz, CDCl3)
d 8.07
nonan-4-one (3f)
Colorless oil; 1H NMR (300 MHz, CDCl3)
d 7.36e7.20 (m, 15H),
(d, J ¼ 8.3 Hz, 2H), 7.50 (d, J ¼ 8.6 Hz, 2H), 7.42e7.37 (m, 5H),
7.13e6.99 (m, 10H), 6.82 (d, J ¼ 8.6 Hz, 2H), 6.71 (d, J ¼ 8.6 Hz, 2H),
3.81 (s, 3H), 3.79 (s, 3H), 3.37 (s, 1H); 13C NMR (75 MHz, CDCl3)
2.94 (s, 1H), 2.28 (t, J ¼ 6.1 Hz, 2H), 1.91e1.73 (m, 2H), 1.68e1.51 (m,
2H), 1.41e1.20 (m, 2H), 0.88 (t, J ¼ 6.4 Hz, 3H), 0.59 (t, J ¼ 6.8 Hz,
3H); 13C NMR (75 MHz, CDCl3)
d 209.2, 144.2, 141.3, 141.2, 140.1,
d
196.7, 163.3, 158.9, 143.6, 142.8, 141.0, 139.5, 136.7, 132.1, 131.5,
131.5, 129.3, 128.9, 128.2, 128.1, 128.0, 127.9, 127.5, 122.6, 91.6, 85.8,
71.6, 47.3, 44.7, 17.4, 16.7, 13.9, 13.3; HRMS (EI) calcd. for C30H30O2,
422.2246, found, 422.2245; IR (KBr) 3469, 3055, 2960, 2223, 1693,
130.8, 129.1, 129.0, 128.5, 128.3, 128.2, 127.7, 127.3, 126.6, 122.5,
113.4, 113.1, 91.2, 87.8, 73.3, 55.3, 55.2; HRMS (EI) calcd. for
C38H30O4, 550.2144, found, 550.2142; IR (KBr) 3452, 3051, 2935,
1597 cmꢀ1
.
1651, 1595 cmꢀ1
.
3.1.7. 2-(Diphenylmethylene)-1,3-di(furan-2-yl)-3-hydroxy-5-
3.1.3. 1,3-Bis(3,4-dimethoxyphenyl)-2-(diphenylmethylene)-3-
hydroxy-5-phenylpent-4-yn-1-one (3c)
phenylpent-4-yn-1-one (3g)
Pink oil; 1H NMR (300 MHz, CDCl3)
d
7.45e7.27 (m, 9H),
7.25e7.10 (m, 9H), 6.35 (s, 1H), 6.16 (s, 1H), 6.08 (s, 1H), 4.31 (s, 1H);
13C NMR (75 MHz, CDCl3)
185.5, 153.1, 147.3, 147.2, 142.1, 141.1,
Yellow solid; m.p. 104e106 ꢁC; 1H NMR (300 MHz, CDCl3)
d 7.84
(d, J ¼ 8.9 Hz, 1H), 7.58 (s, 1H), 7.46e7.32 (m, 5H), 7.25e7.18 (m, 2H),
7.08e6.95 (m, 10H), 6.82 (d, J ¼ 9.1 Hz, 1H), 6.69 (d, J ¼ 8.3 Hz, 1H),
3.90 (s, 3H), 3.87 (s, 3H), 3.86e3.81 (br, 6H), 3.27 (br, 1H); 13C NMR
(75 MHz, CDCl3) d 195.8, 152.2, 147.6, 147.5, 147.2, 139.9, 138.5, 136.2,
130.4, 130.0, 128.1, 127.9, 127.7, 127.4, 127.1, 126.9, 126.7, 126.4, 126.3,
d
139.4, 137.7, 131.6, 129.3, 128.6, 128.5, 128.1, 127.9, 127.8, 127.4, 127.3,
122.1, 121.1, 112.1, 110.5, 109.2, 88.8, 86.5, 68.7; HRMS (EI) calcd. for
C32H22O4, 470.1518, found, 470.1512; IR (KBr) 3482, 3057, 2292,
1726, 1597, 1489, 1390 cmꢀ1
.
3.1.8. 3-Hydroxy-2-(nonan-5-ylidene)-1,3-diphenylnon-4-yn-1-
one (3h)
Colorless oil; 1H NMR (300 MHz, CDCl3)
d
8.20 (d, J ¼ 7.0 Hz, 2H),
7.92 (d, J ¼ 6.8 Hz, 2H), 7.56e7.47 (m, 3H), 7.35e7.29 (m, 3H), 5.46
(s, 1H), 2.48e2.22 (m, 4H), 1.91e1.75 (m, 2H), 1.58e1.41 (m, 2H),
1.38e1.21 (m, 4H), 1.18e1.06 (m, 4H), 0.99e0.90 (m, 5H), 0.74e0.65
(m, 6H); 13C NMR (75 MHz, CDCl3)
d 199.0, 145.6, 139.0, 138.3, 132.9,
129.5, 128.4, 128.2, 128.0, 127.8, 126.8, 126.5, 87.4, 81.5, 72.7, 32.3,
30.6, 30.4, 30.0, 28.7, 23.0, 22.5, 22.0, 18.6, 13.8, 13.7, 13.6; HRMS (EI)
calcd. for C30H38O2, 430.2872, found, 430.2869; IR (KBr) 3481, 3061,
2956, 2931, 1664, 1597, 1379 cmꢀ1
.
3.1.9. 3-Hydroxy-1,3-bis(4-methoxyphenyl)-2-(nonan-5-ylidene)
non-4-yn-1-one (3i)
White solid; m.p. 96e97 ꢁC; 1H NMR (300 MHz, CDCl3)
d
8.18e8.10 (m, 2H), 7.87e7.73 (m, 2H), 6.93 (d, J ¼ 8.1 Hz, 2H), 6.84
(d, J ¼ 7.8 Hz, 2H), 3.85 (s, 3H), 3.78 (s, 3H), 2.40e2.35 (m, 2H),
2.11e1.86 (m, 2H), 1.84e1.76 (m, 3H), 1.67e1.46 (m, 5H), 1.37e1.26
Fig. 2. The molecular structure of compound 4c.

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M. Xie et al. / Journal of Organometallic Chemistry 696 (2011) 3397e3401
(m, 2H), 1.19e0.85 (m, 8H), 0.78e0.72 (m, 6H); 13C NMR (75 MHz,
CDCl3) 197.6, 163.4, 159.1, 141.0, 139.1, 138.1, 131.7, 131.6, 128.3,
7.25e7.19 (m, 4H), 2.58e2.50 (m, 1H), 2.41e2.33 (m, 1H), 2.28e2.18
(m, 2H), 1.55e1.42 (m, 2H), 1.25e1.15 (m, 1H), 0.87e0.73 (m, 4H),
d
113.6, 113.4, 87.0, 81.9, 72.2, 55.4, 55.2, 32,2, 30.6, 30.3, 30.0, 28.7,
23.1, 22.5, 22.0, 18.6, 13.9, 13.7, 13.6; HRMS (EI) calcd. for C32H42O4,
490.3083, found, 490.3085; IR (KBr) 3446, 3062, 2929, 2029, 1653,
0.70 (t, J ¼ 7.2 Hz, 3H); 13C NMR (75 MHz, CDCl3)
d 201.1, 149.2,
144.1, 142.7, 134.5, 131.7, 128.7, 128.6, 127.9, 127.6, 123.5, 123.0, 122.7,
89.7, 81.1, 52.6, 44.9, 41.4, 17.8, 17.0, 13.9, 13.5; HRMS (EI) calcd. for
C30H28O: 404.2140, found, 404.2142; IR (KBr) 3062, 2956, 1965,
1595, 1375 cmꢀ1
.
1676, 1597 cmꢀ1
.
3.1.10. 1,3-Bis(4-chlorophenyl)-3-hydroxy-2-(nonan-5-ylidene)
non-4-yn-1-one (3j)
Acknowledgments
White solid; m.p. 88e90 ꢁC; 1H NMR (300 MHz, CDCl3)
d 8.11 (d,
J ¼ 7.6 Hz, 2H), 7.83 (d, J ¼ 7.2 Hz, 2H), 7.46 (d, J ¼ 8.0 Hz, 2H), 7.33
(d, J ¼ 8.1 Hz, 2H), 2.49e2.28 (m, 2H), 1.92e1.73 (m, 3H), 1.72e1.48
(m, 5H), 1.38e1.20 (m, 3H) 1.19e1.08 (m, 4H), 1.07e0.86 (m, 4H),
The authors are grateful to the National Natural Science Foun-
dation of China (Nos. 20672001 and 20772001) for financial
support of this work. We are also grateful to Prof. Jiping Hu and
Xiaolong Mo for their helpful assistances.
0.85e0.74 (m, 6H); 13C NMR (75 MHz, CDCl3)
d 197.6, 144.2, 139.5,
138.4, 136.7, 133.9, 130.9, 128.8, 128.4, 128.0, 88.3, 81.5, 72.0, 32.4,
30.6, 30.5, 30.1, 29.7, 28.8, 23.1, 22.6, 22.1, 18.6, 13.9, 13.8, 13.6;
HRMS (EI) calcd. for C30H36Cl2O2 (35Cl), 498.2092, found, 498.2095;
Appendix A. Supplementary data
IR (KBr) 3356, 2956, 2225, 1664, 1587 cmꢀ1
.
CCDC 805383 and CCDC 805385 contain the supplementary
crystallographic data for 3a and 4c. These data can be obtained free
of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
The supplementary data associated with this article can be found
in the online version at doi:10.1016/j.jorganchem.2011.07.031.
3.2. General procedure for the synthesis of indenes 4
FeCl3$6H2O (6.8 mg, 0.025 mmol) was added to the solution of
allylic alcohol 3 (0.5 mmol) in CH2Cl2 (2 mL) and the reaction
mixture was stirred at ꢀ20 ꢁC for 5e10 min. After the consumption
of the starting material (monitored by TLC), the reaction mixture
was quenched with saturated NH4Cl and extracted with ethyl
acetate (3 ꢂ 10 mL). The organic layer was combined and dried over
anhydrous Na2SO4. The solvent was evaporated in vacuo and the
crude product was purified by silica gel column chromatography
(silica/hexaneeethyl acetate 10:1 v/v) to obtain products 4.
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d
7.57e7.51 (m, 5H), 7.45e7.39 (m, 5H), 7.36e7.29 (m, 5H), 7.24e7.19
(m, 7H), 7.06 (t, J ¼ 7.5 Hz, 2H); 13C NMR (75 MHz, CDCl3)
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a ¼ 9.2329(7), b ¼ 14.0828(10), c ¼ 21.3326(16) Å;
a
¼ 90,
b
¼ 101.1730(10),
g
l
¼ 90ꢁ. V ¼ 2721.2(3) Å3, T ¼ 293 K, Z ¼ 4, Dc ¼ 1.197 g cmꢀ1
,
m
¼ 0.073 mmꢀ1
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¼ 0.71073 Å; F(000) 1032, 6268 independent reflections (Rint ¼ 0.0274), 23290
reflections collected; refinement method. Full-matrix least-squares on F2;
goodness-of-fit on F2 ¼ 1.029; Final R indices [I > 2
(I)]R1 ¼ 0.0428, wR2 ¼ 0.1133.
s
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c, a ¼ 11.785(3), b ¼ 17.267(4), c ¼ 13.713(3) Å;
a
¼ 90,
b
¼ 103.215(3),
g
m
¼ 90ꢁ.
V ¼ 2716.7(11) Å3,
T ¼ 293
K,
Z ¼ 4,
Dc ¼ 1.324 g cmꢀ1
,
¼ 0.267 mmꢀ1
,
l
¼ 0.71073 Å; F(000) 1120, 6229 independent reflections
(Rint ¼ 0.0274), 23329 reflections collected; refinement method. Full-matrix
least-squares on F2; goodness-of-fit on F2 ¼ 1.035; Final R indices [Io> 2
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