Synthesis and Diels-Alder cycloaddition reaction of norbornadiene and benzonorbornadiene dimers

Article abstract of DOI:10.3762/bjoc.5.39

Dimeric forms of norbornadiene and benzonorbornadiene were synthesized starting with known monobromide derivatives. The Diels-Alder cycloaddition reaction of dimers with TCNE and PTAD was investigated and new norbornenoid polycyclics were obtained. All co

Full text of DOI:10.3762/bjoc.5.39

Synthesis and Diels–Alder cycloaddition reaction of
norbornadiene and benzonorbornadiene dimers
Bilal Nişancı, Erdin Dalkılıç, Murat Güney and Arif Daştan*
Full Research Paper
Open Access
Address:
Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
Atatürk University, Faculty of Science, Department of Chemistry,
25240 Erzurum-TURKEY
doi:10.3762/bjoc.5.39
Received: 12 June 2009
Accepted: 07 August 2009
Published: 11 August 2009
Email:
Arif Daştan* - adastan@atauni.edu.tr
* Corresponding author
Editor-in-Chief: J. Clayden
Keywords:
© 2009 Nişancı et al; licensee Beilstein-Institut.
License and terms: see end of document.
benzonorbornadiene; Diels–Alder reaction; norbornadiene; Stille
coupling
Abstract
Dimeric forms of norbornadiene and benzonorbornadiene were synthesized starting with known monobromide derivatives. The
Diels–Alder cycloaddition reaction of dimers with TCNE and PTAD was investigated and new norbornenoid polycyclics were
obtained. All compounds were characterized properly using NMR spectroscopy.
Introduction
Norbornadiene (1) and related compounds are of great scientific Results and Discussion
interest because of their unusual geometry and high reactivity. One of the starting materials, 2-bromobenzonorbornadiene 4
For example, these compounds exhibit a unique behavior in the was synthesized using a procedure described in the literature
cationic Wagner–Meerwein rearrangement [1-10], in the [15,23] (Scheme 1). Photochemical bromination of benzonor-
solvolytic reactivity [11], in the photochemical di-π-methane bornadiene 2 with 1,2-dibromotetrachloroethane gave isomeric
rearrangement [12-15], as well as in other instances [16-22]. dibromides 3 in high yield. Dehydrobromination reaction of
Therefore, functionalizations of these compounds are important. dibromides 3 with potassium tert-butoxide resulted in the form-
In this study, we investigated the synthesis and Diels–Alder ation of monobromide 4. The other starting material 5 was
cycloaddition reaction of norbornadiene and benzonorbor- obtained using the reported procedures based on the use of
nadiene dimers.
potassium tert-butoxide/n-butyllithium super-base by starting
with commercially available norbornadiene [24-27].
When 2-bromobenzonorbornadiene 4 was treated with n-BuLi
at −78 °C and the resulting anion was quenched with
trimethyltin chloride, a single trimethyltin derivative 6 was
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Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
Scheme 1: Synthesis of starting materials 4 and 5.
observed in the crude reaction mixture and was finally isolated trimethyltin chloride. Reaction of 15 with Cu(NO3)2·3H2O
in 91% yield. Copper salts have been successfully employed for resulted in the formation of dimers 16 and 17 [30]. This reac-
Stille-type hetero-coupling between unsaturated halides and tion offered an alternative synthetic route to norbornadiene
stannanes [28,29]. Treatment of 6 with Cu(NO3)2·3H2O in dry dimers 16 and 17. The isomers 16 and 17 could not be separ-
THF at r.t. afforded the first synthesis of the expected dimers 7 ated, but after cycloaddition reaction of the mixture, the corres-
and 8 in 25% yield in a 3:4 ratio, respectively, besides ponding addition products 18–21 were isolated by chromato-
benzonorbornadiene 2 after column chromatography. The graphic methods (Scheme 3).
Diels–Alder cycloaddition of dimers 7 and 8 with PTAD (9)
and TCNE (10) resulted in the formation of the corresponding Structural Analyses
products 11–14 in high yields (Scheme 2).
The determination of the structures of dimers 7, 8 and dimers
16, 17 by spectroscopic methods was not simple because the Cs
Similarly, tin compound 15 was synthesized by the reaction of symmetry of the syn dimers and the C2 symmetry of the anti
monobromide 5 with n-BuLi followed by reaction with dimers and the free rotation around the central σ bond make
Scheme 2: Synthesis and Diels–Alder cycloaddition reactions of dimers 7 and 8.
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Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
the endo orientation of protons at C3 and C3′, which in turn
proves the exo-orientation of the rings in adduct 11, 12, 18 and
19. The coupling between the protons H3 (H3′) and H7syn
(H7′syn) (M or W orientation) also confirms the exo structures
for 11, 12, 18 and 19 (Figure 1).
In summary, the synthesis and cycloaddition reaction of norbor-
nadiene and benzonorbornadiene dimers was investigated and
new norbornanoid polycyclic compounds, which open up
several synthetic and mechanical investigations, were obtained.
Experimental
General: Melting points are uncorrected. Infrared spectra were
obtained from solution in 0.1 mm cells or KBr pellets on a
regular instrument. The 1H and 13C NMR spectra were recorded
on 400 (100) and 200 (50) MHz spectrometers. Apparent split-
ting is given in all cases. Column chromatography was
performed on silica gel (60-mesh, Merck) TLC was carried out
on Merck 0.2 mm silica gel 60 F254 analytical aluminum plates.
All substances reported in this paper are meso-compounds or
racemates.
Scheme 3: Synthesis and Diels–Alder cycloaddition reactions of
dimers 16 and 17.
Synthesis of (1,4-dihydro-1,4-methano-naphthalen-2-
them indistinguishable. To determine which is which, cycload- yl)trimethylstannane (6): A solution of n-BuLi in n-hexane
dition reactions of dimers are more informative. Dimers 7 and (2.7 M, 3.41 mL, 9.19 mmol) was added dropwise to a solution
16 give symmetric addition products 11, 12 and 18, 19, whereas of monobromobenzonorbornadiene 4 (2.03 g, 9.19 mmol) in dry
the reaction of dimers 8 and 17 resulted in the formation of THF (20 mL) at −78 °C and the resulting mixture was stirred
unsymmetrical products 13, 14 and 20, 21.
for 40 min. Trimethyltin chloride (1.83 g, 9.19 mmol) was
added portionwise and then left to warm to room temperature.
For the symmetric addition products 11, 12, 18 and 19, there are The mixture was stirred overnight at room temperature. The
two possibilities: exo adduct or endo adduct (Figure 1). The crude product was washed with water (15 mL) and extracted
coupling constants between the relevant protons in the with Et2O (2 × 50 mL) and then the combined ethereal extracts
norbornene unit are very informative to assign the correct were dried over MgSO4 and concentrated in vacuo. (1,4-
configuration of the substituents [9,10]. The high value of J34 dihydro-1,4-methano-naphthalen-2-yl)trimethylstannane (6)
and J3′4′ (2.5–3.5 Hz) in the Diels–Alder addition products is was obtained as yellow liquid (2.55 g, 91%). 1H NMR (400
uniquely accommodated by the exo orientation of the protons MHz, CDCl3): δ 7.26–7.20 (m, 2H, aryl), 7.06 (d, J3,4 = 2.9 Hz,
(endo orientation of -A-A- ring) at C3 and C3′ carbon atoms. 1H, H3), 6.98–6.94 (m, 2H, aryl), 4.08 (m, 1H, H4), 3.98 (m,
For example, though there is coupling between the protons H3 1H, H1), 2.24 (m, 2H, H9syn and H9anti), 0.18 (s, 9H, 3 × CH3).
and H4, there is no measurable coupling between the protons 13C NMR (100 MHz, CDCl3): δ 155.61, 153.22, 151.95,
H3′ and H4′ in anti structures (Figure 1). On the other hand, the 151.92, 124.36, 124.18, 121.62, 121.58, 69.65, 55,77, 52.05,
absence of any coupling between the related protons confirms −9.70.
Figure 1: Numbering of carbon atoms and description of possible structures for dimers 11–14 and 18–21.
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Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
Reaction of (1,4-dihydro-1,4-methano-naphthalen-2- Cycloaddition reaction of the dimer 7 with TCNE (10): A
yl)trimethylstannane (6) with Cu(NO3)2·3H2O: Copper(II) solution of the syn dimer 7 (50 mg, 0.17 mmol) and TCNE (10,
nitrate trihydrate (345 mg, 1.4 mmol) was added portionwise to 23 mg, 0.17 mmol) in 5 mL of CH2Cl2 was stirred at room
a solution of 6 (435 mg, 1.4 mmol) in THF (6 mL) at room temperature for overnight. The solvent was removed under
temperature. The blue solution turned green within 1 h. The reduced pressure. The crude product was purified by crystalliza-
crude reaction mixture was diluted with Et2O (100 mL) and tion from CH2Cl2/n-hexane (3:1) to give syn cycloadduct 12 (68
then washed with 5% NH3 (15 mL). The organic phase was mg, 93%). White crystals, mp 230–232 °C. 1H NMR (400
dried over MgSO4 and concentrated in vacuo. The residue was MHz, CDCl3): δ 7.54–7.17 (m, 8H, Haryl), 4.22 (s, 2H), 3.86
chromatographed on neutral aluminum oxide (150 g) eluted (m, 2H), 2.48 (bd, A Part of AB system, 2H, J = 10.3 Hz), 2.45
with hexane. The first fraction was benzonorbornadiene (155 (m, 2H), 2.22 (d, B Part of AB system, 2H, J = 10.3 Hz). 13C
mg, 57%). The second fraction was anti isomer 8 (28 mg, 14%). NMR (100 MHz, CDCl3): δ 145.93, 144.40, 133.14, 127.76,
1H NMR (400 MHz, CDCl3): δ 7.15–6.79 (m, 8H, Haryl), 6.56 127.32, 122.17, 122.06, 112.08, 110.87, 50.01, 48.54, 47.81,
(d, J3,4 = J3′,4′ = 2.9 Hz, 2H, H3 and H3′), 3.92 (m, 2H, H4 and 46.73, 45.90. IR (KBr, cm−1): 3050, 2955, 2872, 2306, 2254,
H4′), 3.86 (m, 2H, H1 and H1′), 2.40 (dt, A Part of AB system, 2217, 1463, 1318, 1265, 1120, 1153, 1013, 981, 785, 704. MS
J9syn,9anti = J9′syn,9′anti = 7.1 Hz, J9syn,1 = J9syn,4 = J9′syn,1′ = (70 eV) m/z: 410.1 (M+, 100), 394.1 (10), 370.1 (37), 345.1
J9′syn,4′ = 1.5 Hz, 2H, H9syn and H9′syn), 2.25 (bd, B part of AB (35), 319.1 (27), 295 (27), 267.1 (45), 265.0 (27), 229.0 (17),
system, J9anti,9syn = J9′anti,9′syn = 7.1 Hz, 2H, H9anti,9′anti).13C 205.0 (32), 176.9 (22), 164.9 (4), 152.9 (22), 151.9 (30).
NMR (100 MHz, CDCl3): δ 151.89, 151.46, 150.65, 133.96,
124.40, 124.32, 121.67, 120.97, 68.76, 52.12, 50.89. The third Cycloaddition reaction of the dimer 8 with PTAD (9): A
fraction was the syn-dimer 7 (23 mg, 11%). Colorless crystals solution of the anti dimer (40 mg, 0.14 mmol) and PTAD (25
from CH2Cl2/n-hexane (1:3). mp 152–154 °C. 1H NMR (400 mg, 0.14 mmol) in 4 mL of CH2Cl2 was stirred at room temper-
MHz, CDCl3): δ 7.29–6.94 (m, 8H, Haryl), 6.61 (d, J3,4 = J3′,4′ = ature for 30 min. The solvent was removed under reduced pres-
2.9 Hz, 2H, H3 and H3′), 3.90 (m, 2H, H4 and H4′), 3.80 (m, 2H, sure. The crude product was purified by crystallization from
H1 and H1′), 2.21 (dt, A Part of AB system, J9syn,9anti = ether/n-hexane (2:1) to give anti cycloadduct 13 (58 mg, 90%).
J9′syn,9′anti = 7.3 Hz, J9syn,1 = J9syn,4 = J9′syn,1′ = J9′syn,4′ = 1.6 Yellow crystals, mp 168–170 °C. 1H NMR (400 MHz, CDCl3):
Hz, 2H, H9anti and H9′anti), 2.17 (bd, B Part of AB system, δ 7.57–7.00 (m, 13H, Haryl), 4.94 (m, 1H), 4.52 (d, J = 2.3 Hz,
J9anti,9syn = J9′anti,9′syn = 7.3 Hz, 2H, H9anti and H9′anti). 13C 1H), 4.38 (m, 1H), 4.09 (m, 1H), 3.34 (m, 1H), 2.40 (dt, A part
NMR (100 MHz, CDCl3): δ 151.88, 151.55, 151.32, 134.38, of AB system, J = 7.7 Hz, J = 1.5 Hz, 1H), 2.36 (dt, B part of
124.59, 124.41, 121.70, 121.15, 67.71, 51.59, 50.72. IR (KBr, AB system, J = 7.7 Hz, J = 1.5 Hz, 1H), 1.43 (bd, A part of AB
cm−1): 3067, 2981, 2936, 2866, 1455, 1317, 1270, 1226, 1199, system, J = 10.7 Hz, 1H), 1.25 (m, 1H), 0.46 (bd, B part of AB
1149, 1068, 1011, 909, 750, 735. MS (70 eV) m/z: 282.5 (M+, system, J = 10.7 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ
32), 267.5 (21), 239.4 (5), 202.4 (2), 178.4 (5), 167.3 (26), 155.20, 154.38, 150.70, 147.28, 147.18, 145.68, 142.93, 129.50,
165.3 (32), 141.2 (28), 117.2 (71), 115.2 (56), 89.1 (6), 63.1 (3). 129.35, 128.80, 128.53, 127.91, 127.53, 125.93, 125.85, 125.62,
125.41, 123.17, 122.43, 121.92, 69.32, 63.91, 62.90, 50.90,
Cycloaddition reaction of the dimer 7 with PTAD (9): A 49.64, 49.53, 49.27, 45.43. IR (KBr, cm−1): 3065, 2961, 2923,
solution of the syn dimer 7 (40 mg, 0.14 mmol) and PTAD (25 2851, 1718, 1497, 1412, 1262, 1135, 1091, 1023, 801. MS (70
mg, 0.14 mmol) in 4 mL of CH2Cl2 was stirred at room temper- eV) m/z: 410.1 (M+, 100), 394.1 (10), 370.1 (33), 345.1 (31),
ature for 30 min. The solvent was removed under reduced pres- 319.1 (26), 267.1 (45), 205.0 (33), 164.9 (44), 151.9 (32).
sure. The crude product was purified by crystallization from
CH2Cl2/n-hexane (3:1) to give syn cycloadduct 11 (55 mg, Cycloaddition reaction of the dimer 8 with TCNE (10): A
89%). Yellow crystals, mp 182–184 °C. 1H NMR (400 MHz, solution of the anti dimer 8 (40 mg, 0.14 mmol) and TCNE (10,
CDCl3): δ 7.60–7.12 (m, 13H), 4.66 (s, 2H), 4.24 (s, 2H), 3.75 18 mg, 0.14 mmol) in 5 mL of CH2Cl2 was stirred at room
(d, J = 1.5 Hz, 2H), 2.21 (dq, A Part of AB system, J = 9.4 Hz, temperature for overnight. The solvent was removed under
J = 1.5 Hz, 2H), 2.14 (dt, B Part of AB system, J = 9.4 Hz, J = reduced pressure. The crude product was purified by crystalliza-
1.4 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ 151.74, 144.59, tion from CH2Cl2/n-hexane (3:1) to give anti cycloadduct 14
144.54, 132.02, 131.84, 129.27, 128.28, 127.38, 127.05, 126.04, (53 mg, 91%). White crystals, mp 240 °C (dec). 1H NMR (400
123.09, 121.94, 59.25, 48.73, 48.20, 47.18. IR (KBr, cm−1): MHz, CDCl3): δ 7.55–7.17 (m, 8H), 4.15 (m, 1H), 4.13 (m,
3048, 2976, 2941, 1762, 1702, 1600, 1502, 1439, 1419, 1343, 1H), 3.92 (dd, J = 3.5 Hz, J = 1.5 Hz, 1H), 3.74 (m, 1H), 3.41
1265, 1140. MS (70 eV) m/z: 458.4 (M+, 3), 344.0 (5), 282.0 (dd, J = 3.5 Hz, J = 1.5 Hz, 1H), 2.52 (m, 1H), 2.31 (dt, A part
(10), 280.8 (7), 165.6 (24), 119.4 (43), 116.4 (100), 91.3 (43). of AB system, J = 9.5 Hz, J = 1.5 Hz, 1H), 2.11 (dt, A part of
AB system, J = 10.3 Hz, J = 1.5 Hz, 1H), 2.06 (dt, B part of AB
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Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
system, J = 9.5 Hz, J = 1.5 Hz, 1H), 2.02 (bd, B part of AB (2:1), mp: 174–176 °C. 1H NMR (400 MHz, CDCl3): δ
system, J = 10.3 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 7.53–7.25 (m, 5H, H), 6.33–6.27 (m, 3H), 6.06 (dd, J = 5.5 Hz,
146.29, 145.79, 144.63, 139.70, 132.89, 132.55, 128.80, 127.61, J = 2.9 Hz, 1H), 4.33 (d, J = 3.6 Hz, 1H), 4.09 (m, 1H), 3.93
127.33, 127.30, 126.60, 122.18, 121.98, 120.73, 112.40, 112.33, (m, 1H), 3.68 (d, J = 1.7, 1H), 3.54 (m, 2H), 1.88 (dt, A part of
109.23, 108.83, 52.93, 50.29, 49.19, 47.86, 47.71, 47.49, 47.43, AB system, J = 9.2 Hz, J = 1.7 Hz, 1H), 1.77 (bd, A part of AB
46.79, 45.12, 44.55. IR (KBr, cm−1): 3049, 2989, 2956, 2923, system, J = 8.8 Hz, 1H), 1.68 (bd, B part of AB system, J = 9.2
2851, 2241, 1906, 1459, 1366, 1262, 1012, 984. MS (70 eV) m/ Hz, 1H), 1.54 (bd, B part of AB system, J = 8.8 Hz, 1H). 13C
z: 410.1 (M+, 40), 345.1 (13), 295.1 (10), 252.0 (7), 205.0 (13), NMR (100 MHz, CDCl3): δ 151.07, 149.85, 136.64, 136.55,
164.9 (12), 127.9 (8), 117.0 (30), 114.9 (100).
135.80, 133.12, 131.90, 131.61, 131.34, 129.20, 128.05, 125.87,
58.26, 56.54, 48.04, 47.57, 46.72, 46.37, 45.59, 45.38. IR (KBr,
Synthesis of (bicyclo[2.2.1]hepta-2,5-dien-2-yl)trimethyl- cm−1): 3060, 2925, 2852, 1760, 1698, 1502, 1419, 1130, 1028,
stannane (15): A solution of n-BuLi in n-hexane (2.5 M, 1.2 721. MS (70 eV) m/z: 357.3 (M+, 19), 315.8 (16), 291.2 (93),
ml, 2.9 mmol) was added dropwise to a solution of 2-bromobi- 250.9 (21), 239.2 (41), 195.1 (22), 182.1 (82), 118.8 (90), 91.0
cyclo[2.2.1]hepta-2,5-diene (5, 0.50 g, 2.9 mmol) in dry THF (5 (77), 77.0 (44). The second fraction was syn-cycloadduct 18 (75
mL) at −78 °C and the resulting mixture was stirred for 1 h. mg, 69% based on syn dimer 16) Yellowish crystals from
Trimethyltin chloride (582 mg, 2.9 mmol) was added portion- CH2Cl2/n-hexane (2:1), mp: 194–196 °C. 1H NMR (400 MHz,
wise and then left to warm to room temperature. The mixture CDCl3): δ 7.54–7.34 (m, 5H, Haryl), 6.28 (m, 4H), 4.10 (m 2H),
was stirred over night at room temperature. The crude product 3.73 (m, 2H), 3.64 (m, 2H), 1.84 (bd, A Part of AB system, J =
was washed with water (50 mL) and extracted with Et2O (2 × 9.0 Hz, 2H), 1.69 (bd, B part of AB system, J = 9.0 Hz, 2H).
50 mL) and then the combined ethereal extracts were dried over 13C NMR (100 MHz, CDCl3): δ 151.47, 136.83, 135.82,
MgSO4 and concentrated in vacuo. (Bicyclo[2.2.1]hepta-2,5- 131.83, 131.05, 129.25, 128.19, 126.06, 57.94, 48.10, 46.20,
dien-2-yl)trimethylstannane (15) was obtained in the form of a 45.66. IR (KBr, cm−1): 3060, 2962, 2929, 2863, 1760, 1700,
yellow liquid (700 mg, 95%). 1H NMR (400 MHz, CDCl3): δ 1502, 1422, 1279, 1139, 761, 729. MS (70 eV) m/z: 357.4 (M+,
7.02 (bd, J3,4 = 2.9 Hz, 1H, H3), 6.70 (m, 1H, H5 or H6), 6.65 4), 316.4 (4), 291.3 (54), 280.1 (3), 252.0 (4), 239.0 (7), 210.3
(m, 1H, H5 or H6), 3.76 (m, 1H, H1 or H4) 3.63 (m, 1H, H1 or (9), 182.1 (25), 165.1 (35), 144.0 (71), 120.0 (16), 115.0 (40),
H4), 1.91 (m, 1H, H7syn or H7anti), 1.88 (m, 1H, H7syn or 102.0 (9), 90.7 (65), 66.1 (23).
H7anti), 0.12 (s, 9H, 3 × CH3).13C NMR (100 MHz, CDCl3): δ
155.46, 154.28, 143.12, 143.07, 74.70, 55.77, 52.15, −9.90.
Cycloaddition reaction of syn-16 and anti-17 mixture with
TCNE (10): A solution of mixture of syn-16 and anti-17 (103
Reaction of (bicyclo[2.2.1]hepta-2,5-dien-2-yl)trimethylstan- mg, 0.56 mmol) and TCNE (10, 72 mg, 0.56 mmol) in 10 mL of
nane (15) with Cu(NO3)2·3H2O: Copper(II) nitrate trihydrate CH2Cl2 was stirred at room temperature overnight. The solvent
(1.13 g, 4.69 mmol) was added portionwise to a solution of 15 was removed under reduced pressure. The residue was chroma-
(1.2 g, 4.69 mmol) in THF (10 mL) at room temperature. The tographed on silica gel (30 g) eluted with EtOAc/n-hexane
blue solution turned green within 40 min. The crude reaction (1:32). The first fraction was anti-1,4,5,8,8a,10a-hexahydro-
mixture was diluted with Et2O (100 mL) and then washed with 1,4:5,8-dimethanophenanthrene-9,9,10,10-tetracarbonitrile (21)
5% NH3 (15 mL). The organic phase was dried over MgSO4 (82 mg, 87% based on anti dimer 17). Yellowish crystals from
and concentrated in vacuo. The syn-dimer 16 and anti-dimer 17 CH2Cl2/n-hexane (3:1), mp:160–162 °C. 1H NMR (400 MHz,
(in a 46:54 ratio) were obtained as a mixture (130 mg, 30%). CDCl3): δ 6.46–6.35 (m, 4H), 3.61 (m, 2H), 3.49 (m, 1H),
The isomeric dimers 16 [30] and 17 [30] could not be separated 3.36–3.33 (m, 2H), 2.36 (m, 1H), 2.16 (d, A part of AB system,
and were used as the mixture for the following step.
J = 9.9 Hz, 1H), 1.95 (d, B Part of AB system, J = 9.9 Hz, 1H),
1.74–1.71 (m, 2H). 13C NMR (100 MHz, CDCl3): δ 138.63,
Cycloaddition reaction of syn-16 and anti-17 mixture with 138.37, 138.27, 132.47, 131.96, 130.76, 113.25, 112.03, 110.50,
PTAD: A solution of mixture of syn-16 and anti-17 (120 mg, 110.47, 51.40, 51.32, 48.01, 46.74, 46.47, 46.43, 45.63, 45.62,
0,66 mmol) and PTAD (116 mg, 0,66 mmol) in 10 mL of 44.79, 44.75. IR (KBr, cm−1): 2934, 2896, 2868, 2352, 2093,
CH2Cl2 was stirred at room temperature for 30 min. The solvent 1457, 1235, 1043, 960. MS (70 eV) m/z: 310.1 (M+, 83), 295.0
was removed under reduced pressure. The residue was chroma- (17), 282.1 (70), 268.0 (57), 243.0 (73), 229.0 (55), 218.1 (80),
tographed on silica gel (30 g) column eluted with EtOAc/n- 203.0 (48), 190.0 (52), 179.0 (40), 167.0 (100), 151.9 (53). The
hexane (1:9).
second fraction was syn-1,4,5,8,8a,10a-hexahydro-1,4:5,8-
dimethanophenanthrene-9,9,10,10-tetracarbonitrile (19) (75 mg,
The first fraction was anti-cycloadduct 20 (89 mg, 70% based 93% based on syn dimer 16). Colorless crystals from CH2Cl2/n-
on anti dimer 17). Yellowish crystals from CH2Cl2/n-hexane hexane (2:1), mp: 136–138 °C. 1H NMR (400 MHz, CDCl3): δ
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Beilstein Journal of Organic Chemistry 2009, 5, No. 39.
17.Lledó, A.; Solà, J.; Verdaguer, X.; Riera, A.; Maestro, M. A.
Adv. Synth. Catal. 2007, 349, 2121–2128.
6.43 (dd, J = 5.5 Hz, J = 3.3 Hz, 2H), 6.30 (dd, J = 5,5 Hz, J =
2.9 Hz, 2H), 3.66 (s, 2H), 3.36 (d, J = 1.3 Hz, 2H), 2.48 (d, J =
1.3 Hz, 2H), 2.10 (d, A Part of AB system, Ji = 9.5 Hz, 2H),
1.89 (d, B Part of AB system, J = 9.5 Hz, 2H). 13C NMR (100
MHz, CDCl3): δ 138.25, 137.78, 132.26, 112.39, 110.79, 49.49,
47.90, 46.52, 45.95, 45.30. IR (KBr, cm−1): 3066, 2995, 2951,
2874, 2247, 1454, 1317, 1007, 727. MS (70 eV) m/z: 310.1
(M+, 35), 282.1 (24), 268.1 (25), 242.1 (27), 228.1 (25), 217.1
(35), 204.1 (18), 189.0 (24), 178.1 (19), 167.1 (38), 126.9 (20),
115.2 (30), 101.3 (14), 91.0 (18), 88.1 (22), 76.1 (18), 65.5
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Acknowledgments
This work has been supported by TUBITAK (project no
106T082), TUBA (Turkish Academy of Sciences, under the
Young Scientist Award Program (AD/TUBA-GEBIP/2001-1-
3)) and Atatürk University. We are indebted for their financial
support.
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