Selective alkylation and Suzuki coupling as an efficient strategy for introducing functional anchors to the ethylene-bis(indenyl) ligand

Article abstract of DOI:10.1016/j.tetlet.2004.12.101

Chiral ansa-ethylene-bis(indenyl)-metal complexes, EBI-MX₂, are useful pre-catalysts for a wide variety of reactions, including hydrogenations, hydrosilylations, and polymerization reactions. In order to immobilize these complexes onto heterogeneous supports, a new methodology was developed to introduce functional anchors to the ethylene-bis(indenyl) ligand, EBI. This was accomplished by selective alkylation of indene to form toluene-4-sulfonic acid 2-(3H-inden-1-yl)-ethyl ester, which was then used to alkylate 6-bromoindene. The selective introduction of an aryl bromide then undergoes coupling reactions with aryl borates via the Suzuki coupling to efficiently introduce an alkenyl or alcohol, functional anchor in a simple four step synthesis.

Full text of DOI:10.1016/j.tetlet.2004.12.101

Tetrahedron
Letters
Tetrahedron Letters 46 (2005) 1353–1356
Selective alkylation and Suzuki coupling as an
efficient strategy for introducing functional anchors to
the ethylene-bis(indenyl) ligand
Anthony P. Panarello, Oleksiy Vassylyev and Johannes G. Khinast*
Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98, Brett Road,
Piscataway, NJ 08854, USA
Received 30 November 2004; revised 18 December 2004; accepted 20 December 2004
Available online 18 January 2005
Abstract—Chiral ansa-ethylene-bis(indenyl)-metal complexes, EBI–MX2, are useful pre-catalysts for a wide variety of reactions,
including hydrogenations, hydrosilylations, and polymerization reactions. In order to immobilize these complexes onto hetero-
geneous supports, a new methodology was developed to introduce functional anchors to the ethylene-bis(indenyl) ligand, EBI. This
was accomplished by selective alkylation of indene to form toluene-4-sulfonic acid 2-(3H-inden-1-yl)-ethyl ester, which was then
used to alkylate 6-bromoindene. The selective introduction of an aryl bromide then undergoes coupling reactions with aryl borates
via the Suzuki coupling to efficiently introduce an alkenyl or alcohol, functional anchor in a simple four step synthesis.
Ó 2005 Published by Elsevier Ltd.
Chiral ansa-ethylene-bis(tetrahydroindenyl)–metal com-
plexes (EBTHI–MX2), first introduced by Brintzinger
and co-workers,1 are highly active catalysts for enantio-
selective reactions, including reductions of olefins, ke-
tones, and imines, as well as various polymerization
reactions.2 Since these organometallic complexes are
homogeneous, they are less attractive for industrial use
than heterogeneous catalysts. Thus, the focus of this
As shown in Scheme 1, our initial approach was the
coupling of 5-bromo-indanone, 1, with 4-(hydroxy-
methyl)phenylboronic acid, 2, to form 5-(40-
hydroxymethyl-phenyl)-indan-1-one, 3, in 98% yield,
using heterogeneous Pd/C as the catalyst and a isopro-
pyl–water solvent mixture.4 Reduction of indanone, 3,
to the indenyl derivative, 4, was accomplished using
standard reduction chemistry5. The terminal alcohol
was then protected with either the TIPS, (triisopropylsi-
lane) 5, or MOM, (methoxymethyl ether) 6 protecting
group.6 Reversing the coupling and reduction sequences
had little impact on the reaction yields as shown for the
preparation of 6-(40-vinylphenyl)-1H-indene and 6-[40-
(hydroxymethyl)phenyl]-1H-indene, 9 and 4, respec-
tively. However, indanone reduction of 1 to form
bromoindene, yielded not only the desired 6-bromoind-
ene, 7, but also small amounts of its 5-isomers, 8.7 Inter-
estingly, none of the indene derivatives, 4, 5, 6, or 9 were
successfully alkylated upon addition to toluene-4-sul-
fonic acid 2-(3H-inden-10-yl)-ethyl ester, 11, 3-(20-
bromoethyl)-1H-indene, 12, or 3-(20-chloroethyl)-1H-
indene, 13, even after numerous modifications of the
alkylation procedure.8 However, alkylation of 7 with
either, 11, 12, or 13 did afford 6-bromo-3-[20-(3H-in-
den-100-yl)-ethyl]-1H-indene, 14, in moderate yields
(59%), with 11 offering the best results and easiest sepa-
ration.9 In addition, compared to the indenyllithium,
work is to develop a strategy for immobilizing
EBTHI–MX2 catalysts onto heterogeneous supports.
We recently reported the preparation of an EBTHI
ligand containing a carbon tether from the cyclohexane
backbone3 and now expand this concept to the more sta-
ble ethylene-bis(indenyl) ligand, EBI. The synthetic
pathway presented herein describes the first successful
approach for introducing functional anchors into the
EBI ligand and offers a methodology for incorporating
a diverse range of functional anchors.
Keywords: Suzuki coupling; Selective alkylation; Indene; Ligand;
Cyclopaentadienyl; Ethylene-bis(indene).
*
Corresponding author. Tel.: +1 732455 9273; fax: +1 732445
2581; e-mail: khinast@soemail.rutgers.edu
0040-4039/$ - see front matter Ó 2005 Published by Elsevier Ltd.
doi:10.1016/j.tetlet.2004.12.101

1354
A. P. Panarello et al. / Tetrahedron Letters 46 (2005) 1353–1356
O
Br
2
O
1
HO
HO
R
3
5
6
R = CH2OTIPS
R = CH2OMOM
4
Br
2 or 10
4
R
1 = CH2OH
Br
9
R1 = CHCH2
R1
7
8
11
12
13
Br
R1
2 or 10
15 R1 = CHCH2
16 R1 = CH2OH
14
Scheme 1. Synthetic pathway of functionalized ethylene-bis(indenyl) ligands.
lithiated 7 was found to be extremely sensitive to mois-
ture contamination.
The investigation of a selectively mono-alkylated indene
intermediate was a critical prerequisite for our synthetic
efforts toward introducing a functional anchor to the
EBI ligand. An overview of the alkylation reactions
are shown in Scheme 2.12 Indene, 17, was first lithiated
using published procedures13, followed by addition to
1,2-di-nucleophilic-ethane, (ethylene glycol di-tosylate,
19, 1,2-dibromoethane, 20, or 1-chloro-2-bromoethane,
21). Small variations in the reaction conditions lead to
significant variations in product distributions. Regard-
less of the starting material, in addition to the desired
mono-alkylated product, observed by-products included
the spiro-product, 22, as well as double alkylation
product, EBI, 23.
Next, coupling 14 with different aryl borates, 2 and 10,
was found to be highly dependent on the reaction condi-
tions and the catalyst. Poor solubility of 14 in an aque-
ous solvent system limited the applicability of the
heterogeneous Pd/C catalyst and did not afford the de-
sired coupling product. Use of palladium acetate, the
ligandless Suzuki coupling catalyst, was also unsuccess-
ful.10 However, the tetrakis(triphenylphosphine)palla-
dium [Pd(PPh3)4] catalyst afforded favorable yields
(40–70%) for the preparation of the 1-[20-(3H-inden-
100-yl)ethyl]-5-(4000-vinylphenyl)-3H-indene (15) and 1-
[20-(3H-inden-100-yl)ethyl]-5-[4000-(hydroxymethyl) phe-
nyl]-3H-indene (16), EBI-derivatives.11 While a THF/
MeOH solvent mixture led to a successful coupling,
when the solvent was replaced with toluene, a common
coupling solvent, the reaction did not afford the desired
product. Both EBI-derivatives, 15 and 16, represent
different functional anchors suitable for immobilizing
organic molecules onto heterogeneous supports.
Alkylation results were most favorable when the inden-
yllithium, 18, was slowly added to the nucleophile.
Reversing the addition sequence resulted in significantly
lower yields of the mono-alkylated products and higher
yields of undesired side products 22 and 23. Addition of
18 to 19 afforded two isolated products: 11, (45%) and
22 (30%). This sequence of addition eliminated the for-
12
13
X
2 = Br
X
2 = Cl
TsO
17
18
BuLi
THF
0oC
OTs
TsO
23
X
X2
2
X
11
1
19
Li
20 X1 = X2 = Br
21 1 = Br, X2 = Cl
18
X
X2
25 X2 = Br
26 2 = Cl
TsO
24
X
22
Scheme 2. Selective mono-alkylation of indene.

A. P. Panarello et al. / Tetrahedron Letters 46 (2005) 1353–1356
1355
mation of 23 as well as the less stable isomer, 24 which is
believed to rapidly convert into the spiro-alkylation
product, 22.
Acknowledgements
We thank Bristol–Myers Squibb for support and Profes-
sor Alan Goldman for helpful discussions.
Addition of indenyllithium, 18, to either 20 or 21 affor-
ded predominately two mono-alkylation isomers, 12 and
13 (70/80%) and 25 and 26 (30/20%) and less than 1% of
23. Mono-alkylation isomers were easily identified by
1H NMR. Although 13 and 26 were readily separated
using flash chromatography, 12 and 25 were unable to
be separated. At this time, the mechanism that results
in the formation of isomers remains unclear, however,
when a catalytic (Cp2ZrCl2 as the catalyst) pathway
was employed a single isomer, 26, was observed
(20%).14 When greater than 10 Mequiv of the alkylating
agent was used, 23 was no longer observed, and decreas-
ing the addition rate minimized the formation of 22.
Lastly, 12 and 13, were found to be much less stable
then 11, even when stored at low temperature.
References and notes
1. Wild, F. R. W.; Zsolnai, J.; Huttner, G.; Brintzinger, H.
H. J. Organomet. Chem. 1982, 232, 233–247.
2. (a) Halterman, R. L. Chem. Rev. 1992, 92, 965–994; (b)
Waymouth, R.; Pino, P. J. Am. Chem. Soc. 1990, 112,
4911–4914; (c) Willoughby, C. A.; Buchwald, S. L. J. Am.
Chem. Soc. 1994, 116, 11703–11714; (d) Verdaguer, X.;
Lange, U. E. W.; Buchwald, S. L. Angew. Chem., Int. Ed.
1998, 37, 1103–1107; (e) Halterman, R. L.; Ramsey, T. M.;
Chen, Z. J. Org. Chem. 1994, 59, 2642–2644; (f) Thayer,
A. M. Chem. Eng. News 1995, 73, 15; (g) Horton, A. D.
Trends Polym. Sci. 1994, 2, 158–166; (h) Tillack, A.;
Lefeber, C.; Peulecke, N. Tetrahedron Lett. 1997, 38,
1533–1534.
Yields and properties of all obtained compounds are
presented in Table 1.
3. Panarello, A. P.; Khinast, J. G. Tetrahedron Lett. 2003,
44, 4095–4098.
4. The Suzuki coupling was carried using slightly modified
procedure from Marck, G.; Villiger, A.; Buchecker, R.
Tetrahedron Lett. 1994, 35, 3277–3280, 1 or 7 (5.62mmol,
1 Mequiv), aryl boronic acid (6.58 mmol, 1.3 Mequiv)
were charged to a 100 mL reaction flask containing 50 mL
of an isopropyl alcohol (10% v/v) and water reaction
solvent. Na2CO3 (2.25 Mequiv) and Pd/C catalyst
(5 mol %, Degussa E1002XU/W, 5 wt%, dry basis, on
50% wet activated carbon) were then added to the reaction
flask. The reaction was then placed in a 75 °C oil bath and
monitored by either HPLC or TLC, where the aryl
bromide was completely consumed in less than 1 h. After
allowing the reaction to cool to room temperature, the
reaction was diluted by adding additional (50 mL) reac-
tion solvent followed by filtering off the Pd/C catalyst.
5. Polo, E.; Bellabarba, R. M.; Prini, G.; Traverso, O.;
Green, M. L. H. J. Organomet. Chem. 1999, 577, 211–218.
6. Compound 5: Imidazol, TIPS-Cl, THF 12h; 6:
MOMOM, LiBr, p-TsOH, 12h. Green, T. W.; Wuts, P.
G. M. Protective Groups in Organic Synthesis, 3rd ed.;
Wiley: New York, 1999.
In conclusion, the four-step synthetic methodology de-
scribed above offers a favorable and convenient strategy
for introducing functional anchors into the EBI ligand.
The use of Suzuki coupling further expands the scope
of this pathway, due to the broad reactivity of aryl bro-
mides with alkenylborates. Ligand development repre-
sents the first step in the engineering of heterogeneous
catalysts. The next step is the introduction of an active
metal species (Ti or Zr) to the functionalized EBI ligand,
followed by immobilization of the active catalytic
complex onto a heterogeneous support. Using terminal
alkenes, immobilization can be accomplished by hydro-
silylation reactions with silica or silica-containing mate-
rials having surface Si–H groups. Furthermore,
hydroxyl-terminated complexes can be anchored using
an esterification reaction procedure. In both cases, it is
necessary to pre-treat the various heterogeneous
surfaces (i.e., silica or alumina) before immobilizing
the complexes.
7. (1) LiAlH4, EE, 0 °C 2h; (2) p-TsOH (cat.), benzene,
75 °C 2h Boyd, D. R.; Sharma, N. D.; Bowers, N. I.;
Boyle, R.; Harrison, J. S.; Lee, K.; Bugg, T. D. H.;
Gibson, D. T. Org. Biomol. Chem. 2003, 1, 1298–1307.
8. Yang, Q.; Jensen, M. D. Synlett 1996, 147–148.
9. (1) BuLi, THF, 0 °C 2h; (2) THF, rt, 12h.
Table 1. Indene derivatives15
#
Product
Eluent (Rf)
Yield, %
10. Badone, D.; Baroni, M.; Cardamone, R.; Ielmini, A.;
Guzzi, U. J. Org. Chem. 1997, 62, 7170–7173.
3
4
Yellow crystals16
Yellowish solid
—
Hexane/EE, 1:2(0.25)
98
90 (from 3)
95 (from 7)
11. The Suzuki coupling reaction using Pd(PPh3)4. In an oven-
dried reaction flask equipped with a reflux head and a stir
bar, Pd(PPh3)4 (5 mol %), aryl boronic acid (0.32mmol,
1.3 Mequiv), and 14 (0.25 mmol, 1 Mequiv) were charged
to a solution of THF and MeOH (4:1, 4 mL). The mixture
was allowed to stir at room temperature while aqueous
K2CO3 (2.0 M, 3.3 Mequiv) was added. The reaction was
then placed in an oil bath and refluxed for 6 hours. The
reaction was quenched at room temperature by adding
water (25 mL) and CH2Cl2 (25 mL). A liquid–liquid
extraction was performed, where the organic phase was
collected and dried with MgSO4. The reaction mixture was
then purified by silica gel chromatography to afford the
desired coupling product: Bosanac, T.; Wilcox, C. S. J.
Am. Chem. Soc. 2002, 124, 4194–4195; Baleizao, C.;
Gigante, B.; Das, D.; Alvaro, M.; Garcia, H.; Corma, A.
5
6
7
9
Light yellow oil
Yellow oil
Hexane (0.3)
93
82
90
80
45
75
80
Hexane/EE, 5:2(0.5)
Hexane/EE, 100:1 (0.6)
Hexane/EE, 50:1 (0.35)
Hexane/EE, 5:2(0.35)
Hexane (0.65)
Yellowish oil7
White solid
11 Dark reddish oil
12 Colorless oil
13 Light yellow oil
14 Light yellow oil
15 Yellow crystals
Hexane (0.6)
Hexane/EE, 100:1 (0.25) 59
Hexane/EE, 50:1 (0.35) 71
78
16 Orange-yellow oil Hexane/EE, 5:2(0.55)
22 Yellowish oil17
23 Yellowish oil13
25 Yellowish oil
26 Colorless oil
Hexane/EE, 100:1 (0.4)
Hexane/EE, 50:1 (0.3)
Hexane/EE, 50:1 (0.35)
Hexane/EE, 50:1 (0.35)
Variable
Variable
Variable
Variable

1356
A. P. Panarello et al. / Tetrahedron Letters 46 (2005) 1353–1356
Chem. Commun. 2003, 1860–1861; Kotha, S.; Lahiri, K.;
126.7, 126.6, 125.3, 123.9, 123.7, 122.4, 121.1, 119.6, 113.9,
113.7, 113.6, 39.2, 38.8. IR (mmax, cmꢀ1, NaBr): 3430, 2924,
1699, 1605, 1398, 1073, 908, 818 (C@C), 733, 698, 623–510
(ter-C@C). Toluene-4-sulfonic acid 2-(3H-inden-10-yl)-
ethyl ester (11).1H NMR (d, CDCl3): 7.83 (d, 1H), 7.73
(d, 2H), 7.45–7.35 (dd, 2H), 7.28 (d, 2H), 7.23 (d, 1H), 6.25
(s, 1H), 4.33 (t, 2H), 3.29 (s, 2H), 2.95 (t, 2H), 2.45 (s, 3H).
13C NMR (d, CDCl3): 144.7, 144.3, 144.1, 138.7, 130.5,
129.8, 127.8, 126.2, 124.9, 123.9, 118.6, 68.7, 37.9, 37.9,
Sreenivasachary, N. Synthesis 2001, 1932–1934; Shultz, D.
A.; Gwaltney, K. P.; Lee, H. J. Org. Chem. 1998, 63, 769–
774.
12. General procedure of indene alkylation. Under argon,
indene and dry THF (20 Mequiv) were charged to an oven
dried reaction flask and placed in an ice bath. BuLi (1.6 M,
1 Mequiv) was dropwise added yielding a deep red
solution. The reaction mixture was then allowed to slowly
warm up to room temperature over 1 h. A second flask
was purged with argon and charged with the appropriate
alkylating agent (1.05 Mequiv) and THF (40 Mequiv).
The indenyllithium solution was then dropwise added to
the alkylating agent at room temperature using a syringe
pump (15 mL/h). A syringe pump allowed for better
control of the addition rate, which proved critical for the
selective alkylation reactions. The reaction was then
allowed to stand over night at room temperature and
quenched the following morning using an saturated
aqueous NH4Cl solution. CH2Cl2 was added and a
liquid–liquid extraction was performed. The organic phase
was then collected and dried with MgSO4. The solvent was
removed under reduced pressure, and obtained oil was
purified by Flash Column Chromatography with elution
by hexane or its mixture with ethyl ether (EE).
27.5, 21.7. MS (m/z): 337 (M++Na+). IR (mmax, cmꢀ1
,
NaBr): 3065–20 (m), 2959–2856 (m), 1709, 1598, 1461,
1359 (S@O), 1176 (S–Ph), 1096, 980–960, 904, 771, 662. 3-
(20-Bromoethyl)-1H-indene (12). 1H NMR (d, CDCl3):
7.5–7.2 (m, 4H), 6.38 (s, 1H), 3.72 (t, 2H), 3.39 (s, 2H),
3.18 (t, 2H). 13C NMR (d, CDCl3): 144.3, 144.2, 137.5,
129.9, 124.9, 124, 122.9, 118, 34.7, 31.5, 30.6. 3-(20-
Chloroethyl)-1H-indene (13). 1H NMR (d, CDCl3): 7.45
(d, 1H), 7.4–7.3 (m, 2H), 7.2–7.25 (t, 1H), 6.35 (s, 1H),
3.73 (t, 2H), 3.39 (s, 2H), 3.05 (t, 2H). 13C NMR (d,
CDCl3): 144.6, 140.4, 130, 126.2, 124.9, 123.9, 118.6, 42.7,
37.9, 31.3. 6-Bromo-3-[20-(3H-inden-100-yl)-ethyl]-1H-ind-
1
ene (14). H NMR (d, CDCl3): 7.45 (d, 1H), 7.4 (d, 2H),
7.35 (s, 2H), 7.25 (d, 2H), 6.29 (s, 2H), 3.35 (s, 4H), 2.95 (s,
4H). 13C NMR (d, CDCl3) 147.7, 146.6, 145.3, 144.5,
143.9, 143.7, 143.6, 143.2, 129.7, 129.1, 128.4, 128.1, 127.3,
127.1, 126.1, 125.1, 124.7, 123.9, 122.2, 120.3, 120.1, 118.9,
118.8, 37.8, 37.7, 37.5, 26.2, 26.1. IR (mmax, cmꢀ1, NaBr):
3063, 2902, 1599, 1563, 1459, 1396, 1273, 1245, 1230, 1202,
1168, 1121, 1059, 1014, 967, 917, 863 (C@C), 809 (C@C),
773 (C@C), 719 (C@C). Elemental analysis (%): C20H17Br,
C: 71.2(calcd), 69.32(found), H: 5.08 (calcd), 5.07
(found). 1-[20-(3H-Inden-100-yl)ethyl]-5-(4000-vinylphenyl)-
3H-indene (15). Mp (°C): 104 (hexane). 1H NMR (d,
CDCl3): 7.75 (s, 1H), 7.6 (d, 2H), 7.59 (d, 1H), 7.5 (dd,
4H), 7.45 (t, 1H), 7.35 (t, 1H), 7.25 (t, 1H), 6.85–6.75 (q,
1H), 6.35 (d, 2H), 5.85–5.78 (d, 1H), 5.32–5.25 (d, 1H),
3.45–3.39 (d, 4H), 2.9 (s, 4H). 13C NMR (d, CDCl3):
197.9, 145.3, 144.8, 144.5, 144.1, 144, 137.3, 136.5, 136.2,
128.5, 128, 127.4, 127.2, 126.6, 126, 125.1, 124.6, 123.8,
13. Collins, S.; Bradly, A.; Taylor, N. J.; Ward, D. G. J.
Organomet. Chem. 1988, 342, 21–29.
14. Armus, J.; Kolis, S. P.; Hoveyda, A. H. J. Am. Chem. Soc.
2000, 122, 5977–5983, Used a similar procedure and
replaced the alkenyl-tosylate with 2-chloroethyl p-
toluenesulfonate.
15. Analytical data. 5-(40-Hydroxymethyl-phenyl)-indan-1-
one (3). Mp (°C): 156 (THF). 1H NMR (d, CDCl3): 7.9
(d, H), 7.7–7.55 (m, 4H), 7.45 (d, 2H), 4.75 (s, 2H), 3.2 (t,
2H), 2.78 (t, 2H), 1.75 (br s, 1H). 13C NMR (d, CDCl3):
155.9, 147.3, 141.1, 139.5, 136, 127.7, 127.5, 126.7, 125.1,
124.1, 64.9, 36.5, 25.9. MS (APPI, m/z): 261 (M++Na+).
IR (mmax, cmꢀ1, NaBr): 3380 (OH), 2925–2825, 1682
(C@O), 1608, 1440, 1405, 1300, 1199, 1111, 1058, 799, 636.
6-[40-(Hydroxymethyl)phenyl]-1H-indene (4). 1H NMR (d,
CDCl3): 7.73 (s, 1H), 7.65 (d, 2H), 7.55–7.45 (m, 4H), 6.95
(d, 1H), 6.6 (d, 1H), 4.75 (d, 2H), 3.49 (s, 2H), 1.65 (t, 1H).
13C NMR (d, CDCl3): 144.5, 144.2, 141.2, 139.4, 137.4,
134.7, 131.8, 127.5, 127.3, 125.5, 122.6, 121.1, 65.2, 39.2.
122.5, 119.1, 118.9, 113.6, 37.9, 37.8, 26.3 IR (mmax, cmꢀ1
,
NaBr): 3049, 2920, 1715, 1603 (C@C), 1460, 1396, 1265,
1167, 1060, 914, 821, 770, 736. 1-[20-(3H-Inden-100-
yl)ethyl]-5-[4000-(hydroxymethyl) phenyl]-3H-indene (16).
1H NMR (d, CDCl3): 7.79–7.72(m, 1H), 7.7–7.65 (m-t,
3H), 7.55–7.45 (m, 5H), 7.35 (d, 1H), 7.25 (d, 1H), 6.3 (br
s, 2H), 4.75 (s, 2H), 3.45–3.75 (dd, 4H), 3.0 (d, 4H), 2.2(br
s, 1H). 13C NMR (d, CDCl3): 146.2, 145.2, 144.5, 144.1,
144, 143.7, 141.3, 139.5, 139.1, 129.9, 128.7, 128.5, 128.1,
128, 127.5, 127.4, 127.3, 126, 125.2, 124.6, 124, 123.8,
123.8, 122.6, 119.1, 118.9, 117.6, 66.7, 37.9, 37.8, 26.3,
26.2. IR (mmax, cmꢀ1, NaBr): 3427 (OH), 2924, 2854, 1699,
1604, 1580, 1541, 1470, 1362, 1176, 1045 (OH), 1013 (OH),
919, 816 (C@C), 769 (C@C), 664, 554. 1-(20-Bromoethyl)-
MS (m/z): 108 (BzOH+), 116 (Ind+). IR (mmax, cmꢀ1
,
NaBr): 3335–3240 (OH), 2920–2860, 1613, 1465, 1405,
1120, 1050 (–OH), 1010, 806 (C@C), 682. 6-{40-[(Triiso-
1
propylsiloxy)methyl]phenyl}-1H-indene (5). H NMR (d,
CDCl3): 7.75 (s, 1H), 7.63 (d, 2H), 7.57 (d, 1H), 7.5–7.4
(d(s), 3H), 6.95 (d, 1H), 6.6 (d, 1H), 4.95 (s, 2H), 3.49 (s,
2H), 1.15 (d, 3H), 1.05 (br s, 18H). 13C NMR (d, CDCl3):
144.5, 144.2, 140.6, 140.5, 138, 134.7, 132, 127.2, 125.6,
122.8, 121.3, 65.1, 39.4, 18.3, 17.9, 12.3. MS (APPI, m/z):
237, 379 (M+). 6-{40-[(Methoxymethoxy)methyl]phenyl}-
1
1H-indene (25). H NMR (d, CDCl3): 7.55–7.25 (m, 4H),
1
1H-indene (6). H NMR (d, CDCl3): 7.7 (s, 1H), 7.6 (d,
6.93 (d, 1H), 6.6 (d, 1H), 3.78 (t, 1H), 3.45 (t, 2H), 2.52–2.4
(m, 1H), 2.25–2.1 (m, 1H). 13C NMR (d, CDCl3): 146.3,
141.3, 131.9, 129.9, 126.9, 126.2, 125.1, 121.3, 49.6, 37.9,
31.6. 1-(20-Chloroethyl)-1H-indene (26). 1H NMR (d,
CDCl3): d 7.45 (d, 1H), 7.4 (d, 1H), 7.35–7.2(m, 2H),
6.85 (d, 1H), 6.55 (d, 1H), 3.7 (t, 1H), 3.6 (t, 2H), 2.4–2.27
(m, 1H), 2.15–2.0 (m, 1H).
2H), 7.55–7.42 (m, 4H), 6.95 (dt, 1H), 6.6 (dt, 1H), 4.75 (s,
2H), 4.65 (s, 2H), 3.55 (s, 3H), 3.45 (s 2H). 13C NMR (d,
CDCl3): 144.4, 144.2, 141.3, 137.5, 136.4, 134.7, 131.7,
128.4, 127.2, 125.5, 122.6, 121.1, 95.7, 69, 55.4, 39.2. IR
(mmax, cmꢀ1, NaBr): 2960–30, 2865, 1761, 1644, 1598,
1467, 1368, 1291, 1181, 1089 (MOMO), 1046, 958, 813
(C@C), 767, 661. 6-(40-Vinylphenyl)-1H-indene (9). 1H
NMR (d, CDCl3): 7.73–7.65 (d, 1H), 7.6 (d, 2H), 7.6–7.55
(m, 1H), 7.5 (d, 2H), 7.48–7.45 (m, 2H), 6.95 (t, 1H), 6.83–
6.73 (q, 1H), 6.62(t, 1H), 5.85–5.75 (d, 1H), 5.3–5.28 (d,
1H), 4.0–3.95 (d, 2H). 13C NMR (d, CDCl3): 145.6, 144.4,
144.2, 142.9, 141.3, 141.2, 139.2, 137.3, 136.5, 136.4, 136.3,
136.2, 134.9, 134.7, 132.1, 131.8, 127.4, 127.3, 127, 126.9,
16. Compound 3 was purified by the addition of THF to the
reaction mixture followed by a liquid–liquid extraction
where the organic phase was collected, dried with MgSO4,
and concentrated.
17. The isolated product confirms to previously published
results: Kauffman, T.; Berghus, K.; Rensing, A. Chem.
Ber. 1985, 118, 3737–3747.