Ruthenium-catalyzed cascade reactions of diynes with norbornadiene -synthesis of norbornene derivatives

Article abstract of DOI:10.1002/ejoc.200901039

Norbomene derivatives 7-11 were prepared from norbornadiene and the corresponding diynes by Ru-catalyzed [(2+2)+2] cycloaddition and subsequent transfer hydrogenation. The structure and stereochemistry of the cycloadducts were confirmed by X-ray crystal a

Full text of DOI:10.1002/ejoc.200901039

FULL PAPER
DOI: 10.1002/ejoc.200901039
Ruthenium-Catalyzed Cascade Reactions of Diynes with Norbornadiene –
Synthesis of Norbornene Derivatives[‡]
Chu-Chun Cheng,[a] Chia-Sen Chang,[a] Yu-Lin Hsu,[a] Ting-Yu Lee,[b] Ling-Chueh Chang,[b]
Shih-Hsien Liu,[c] and Yao-Ting Wu*[a]
Dedicated to Professor Pei-Lin Wu on the occasion of her 60th birthday
Keywords: Norbornadiene / Norbornene / Cascade reaction / Ruthenium / Transfer hydrogenation / Cycloaddition
Norbornene derivatives 7–11 were prepared from norborna-
investigated. Compounds that contained the skeleton of 1,7-
diene and the corresponding diynes by Ru-catalyzed [(2+2)+2] diaryl-1,6-heptadiynes were suitable starting materials. Ad-
cycloaddition and subsequent transfer hydrogenation. The
structure and stereochemistry of the cycloadducts were con-
firmed by X-ray crystal analysis. This procedure provides
high diastereoselectivity to generate norbornenes 7–11 in up
to 82% yield. The scope and limitations of this reaction were
ditionly, 9h was empolyed in the synthesis of polynorbornene
31 by ring-opening metathesis polymerization (ROMP). The
number-average molecular weight (Mn) and polymer-distri-
bution index (PDI) of this new polymer were determined to
be 28.6 kDa and 1.35, respectively.
pound to be more reactive than other simple alkenes and
norbornenes.[5] Alkynes should be ideal reaction partners
for NBD, and numerous examples have been reported
(Scheme 1).[6] Pauson–Khand conditions yield cyclopen-
tenone 1 by a formal [2+2+1] cycloaddition of NBD, an
alkyne and CO.[7] The reaction of NBD and one alkyne
molecule affords a formal [2+2] adduct 2[8] or a homo-
Diels–Alder product 3,[9] depending on the catalysts and
alkynes used. Tetracycles 4 can be obtained by a formal
Introduction
Norbornene is a bridged olefin with a rigid skeleton. The
ring strain (17.6 kcal/mol)[1] makes the double bond in this
molecule reactive. Norbornenes are suitable precursors for
the ring-opening metathesis polymerization (ROMP)[2] be-
cause release of this ring strain drives this process. There-
fore, norbornenes have been widely utilized in the synthesis
of ROMP polynorbornenes. Norsorex®,[3] a polynorbor-
nene, exhibits special properties, such as flexibility, bending
and damping, and can be used for applications in fluid re-
sistant devices and shock absorbers.[4] The preparation of
norbornenes from norbornadiene (NBD) should be a sim-
ple and efficient method because the through-space interac-
tion between the proximal olefins in NBD causes this com-
[‡] Metal-Catalyzed Reactions of Alkynes, IV. Part III: Y.-T. Wu,
M.-Y. Kuo, Y.-T. Chang, C.-C. Shin, T.-C. Wu, C.-C. Tai, T.-
H. Cheng, W.-S. Liu, Angew. Chem. 2008, 120, 10039–10042;
Angew. Chem. Int. Ed. 2008, 47, 9891–9894. Part II: Y.-T. Wu,
W.-C. Lin, C.-J. Liu, C.-Y. Wu, Adv. Synth. Catal. 2008, 350,
1841–1849.
[a] Department of Chemistry, National Cheng-Kung University,
No. 1 Ta-Hsueh Road, 701 Tainan, Taiwan
Fax: +886-6-2740552
E-mail: ytwuchem@mail.ncku.edu.tw
[b] Department of Applied Chemistry, National University of
Kaohsiung,
No. 700 Kaohsiung University Rd., 811 Kaohsiung, Taiwan
[c] Material and Chemical Research Laboratories, Industrial Tech-
nology Research Institute,
195 Chung Hsing Rd., Sec. 4 Chu Tung, 310 Hsin Chu, Taiwan
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200901039.
Scheme 1. Metal-catalyzed/mediated reactions of NBD with
alkynes. Cp = cyclopentadiene.
672
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 672–679

Ruthenium-Catalyzed Cascade Reactions of Diynes with Norbornadiene
[2+2+(2+2)] cycloaddition of NBD and two alkynyl moie-
Compound 7 should be generated by transfer hydrogena-
ties under catalysis by a nickel(II)[10] or rhodium(I) com- tion of the intermediate 6, and iPrOH provided the two
plex.[11] NBD can also act as a “pre-alkyne”.[12] A rhodi- additional hydrogen atoms (5-H and 10-H) in 7a (see
um(I)-catalyzed [(2+2)+2] cycloaddition of NBD with a di- Scheme 4).[15,16] A control experiment confirmed this hy-
yne form the intermediate 6, which subsequently undergoes pothesis. When we performed a reaction in [D8]iPrOH, we
a thermal elimination of cyclopentadiene to give benzene isolated cycloadduct 7a-D2 with a 94% isotope purity
derivatives 5.[11] Recently, we observed that new cycload- (Scheme 2). Ru catalysts are well known to be very efficient
ducts 7–11 can be directly prepared with high diastereo- in catalyzing the formation of a C–C bond[17] or transfer
selectivity from NBD and a diyne in a single pot. In this hydrogenation,[15] but both functions of a Ru catalyst in a
study, the reaction conditions are optimized, and the scope reaction have never been reported before to the best of our
and limitations of this reaction are investigated.
knowledge. Additionally, 7a contains six stereogenic centers
and should be difficult to be produced by other synthetic
methods. For example, the generation of 7a by a Diels–
Alder reaction[18,19] of diene 14[20] with NBD is inefficient.
Results and Discussion
Limited systematic studies of the reaction conditions for
the synthesis of norbornene derivative 7a from diyne 12a
and NBD demonstrated that iPrOH and p-xylene both had
key roles in this reaction (Table 1). In the absence of iPrOH,
we isolated a mixture of 7a (13%), 12a (30%) and 13a (3%,
Table 1, Entry 1). However, a reaction in iPrOH was very
inefficient, and we recovered most of the starting material
12a. We also examined the catalytic abilities of some Ru
complexes. In fact, [RuCl2Cp*]2 (Cp* = 1,2,3,4,5-penta-
methylcyclopentadienyl) and [RuCl2(η4-NBD)]ϱ were ef-
ficient catalysts. Other complexes, such as [RuCl2(2,2Ј-
bipy)]·2H2O and [RuCl2(η6-p-MeC6H4iPr)]2, did not yield
the desired cycloadduct 7a. Notably, the commercially avail-
able polymer form, [RuCl2Cp*]ϱ,[13] was less reactive than Scheme 2.
its dimer analogue [RuCl2Cp*]2. We had to conduct the re-
action with 5 mol-% of catalyst [RuCl2Cp*]2 in a mixed sol-
vent of p-xylene and iPrOH at 130 °C for the best yield.
We investigated the reactivity of several diynes, such as
Under the optimized reaction conditions, we obtained 7a in 3,4-diethynylacenaphthalenes 12, 3,4-diethynylfluoranthene
74% yield (Entry 3 in Table 1), and we did not observe 16 and 1,6-heptadiynes 17–19, in the above-mentioned reac-
other stereoisomers in significant amounts. The structure tion. They provided cycloadducts 7–11 in 21–82% yield
and stereochemistry of 7a were determined from the 2D (Scheme 3 and Table 2). Both rigid and flexible diynes were
NMR spectra. The central cyclohexenyl ring in this com- suitable starting materials. Fluoranthenediyldiyne 16a gave
pound is connected to the exo face of the norbornene moi- a lower yield than did acenaphthalenediyldiyne 12a, per-
ety. The two phenyl substituents at C-5 and C-10 and 5a-H haps because of its low solubility in the mixed solvent sys-
and 9a-H are all cis to each other.[14]
tem. Among 1,6-hepatadiynes, heteroatom-unsubstituted
Table 1. Optimization of reaction conditions for the preparation of norbornene derivative 7a.
Entry
Catalyst (mol-%)
Solvent[a]
Temp. [°C]
Time [h]
Yield [%]
1
2
3
4
5
6
7
8
9
[RuCl2Cp*]2 (5)
[RuCl2Cp*]2 (5)
[RuCl2Cp*]2 (5)
[RuCl2Cp*]2 (5)
[RuCl2Cp*]2 (2.5)
A
B
C
C
C
C
C
C
C
130
130
130
80
130
130
130
130
130
87
68
68
63
63
87
63
63
63
13[b]
trace[c]
74
0[c]
52
56
[RuCl2Cp*]ϱ (5)
[RuCl2(η4-NBD)]ϱ (5)
[RuCl2(2,2Ј-bipy)]·2H2O (10)
[RuCl2(η4-p-MeC6H4iPr)]2 (5)
70
0[c]
0[c]
[a] A: p-xylene, B: iPrOH, C: p-xylene + iPrOH. [b] 30% of 12a and 3% of 13a were also obtained. [c] Most of 12a (Ͼ80%) was recovered.
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673

Y.-T. Wu et al.
Yield [%]
FULL PAPER
17 and 19 provided better results than their ether analogues Table 2. Synthesis of norbornenes 7–11.
18. The Thorpe–Ingold effect[21] was not important in this
Entry
Diyne
R
Product
reaction because 17e and 19e gave the corresponding cy-
cloadducts in similar yields (Entries 10 and 17 in Table 2).
Apparently, only diaryl-substituted diynes could participate
in this reaction. Terminal diyne 17j[22] and dialkyl-substi-
tuted diyne 12f did not furnish the desired cycloadducts.
The former left the starting material unchanged, and the
latter gave a mixture of 13f and a formal [(2+2)+2] cycload-
duct 15. However, 1,7-bis(perfluorophenyl)-1,6-diyne 17i
did not yield norbornene 9i, although 3,4,5-trifluorophenyl-
substituted diyne 17e gave cycloadduct 9e in 59% yield (En-
tries 10 and 13 in Table 2).
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
12a
12b
12c
12d
12e
12f
16a
17a
17d
17e
17g
17h
17i
Ph
3,5-(H3C)2C6H3
4-H3CC6H4
4-FC6H4
3,4,5-F3C6H2
nBu
7a
7b
7c
7d
7e
7f
74
62
34
38
53
0[a]
54
82
23
59
52
42
0[b]
0[c]
51
21
62
Ph
Ph
4-FC6H4
8a
9a
9d
9e
9g
9h
9i
3,4,5-F3C6H2
4-H3CO2CC6H4
4-F3CC6H4
C6F5
17j
H
9j
17k
18k
19e
4-H3COC6H4
4-H3COC6H4
3,4,5-F3C6H2
9k
10k
11e
[a] A mixture of 13f (15%) and 15 (30%) was obtained. [b] Most
of 17i remained unchanged. [c] Due to the low boiling point of
diyne 17j, it could not be recovered.
Figure 1. Molecular structures of 9e (top) and 9h (bottom), show-
ing 50% probability ellipsoids. Except for 4-, 4a-, 8a- and 9-H,
hydrogen atoms have been omitted for clarity.[23]
Scheme 3. Synthesis of norbornenes 7–11. For details, see Table 2.
Based on the control experiment and the relevant litera-
As stated above, diynes that contain a 1,7-diaryl-1,6-hep- ture, a possible mechanism of the formation of 9 was for-
tadiyne skeleton are able to generate cycloadducts 7–11 mulated as shown in Scheme 4. Initially, NBD reduces com-
with the formation of new five- and six-membered rings. plex [RuCl2Cp*]2 to generate the active catalyst 25,[24]
Other species of alkynes did not produce the desired com- which then forms π complex 26 by the replacement of NBD
pounds. For example, 1,2-diphenylethyne gave cyclobutene with diyne 17. The incorporation of a molecule of NBD
2 (RA = RB = Ph) in 46% yield. 1,2-Bis(2-thiophenylethy- leads complex 26 to rearrange to 1-ruthenacyclopentadiene
nyl)-4,5-dimethylbenzene can be regarded as a monoalkyne 27,[17a] where NBD provides its exo face as an η2 li-
in this reaction, forming the [2+2] cycloadduct 21 (56% gand.[25,26] Subsequently, complex 27 inserts NBD to afford
yield), instead of 20 (Scheme 3). Under the reaction condi- the σ complex 24 (route A). Reductive elimination yields
tions used herein, 1,8-diphenyl-1,7-octadiyne did not yield 1,3-cyclohexadiene derivative 23,[27] where the Ru fragment
the corresponding cycloadduct, and we recovered most of is exo to the norbornene moiety. Cyclopentadiene is not
this starting material. X-ray diffraction analysis of cycload- easily released from metal-stabilized intermediate 23, which
ducts 9e and 9h confirmed the structure and stereochemis- prefers to yield 22 by stereoselective transfer hydrogenation
try (Figure 1).[23]
at the cyclohexadiene ring, and iPrOH is oxidized to ace-
674
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Eur. J. Org. Chem. 2010, 672–679

Ruthenium-Catalyzed Cascade Reactions of Diynes with Norbornadiene
Scheme 4. Proposed mechanism of the reaction of diyne 17 and NBD.
data were collected with a Stoe–Siemens-AED diffractometer.
Melting points were determined with a Büchi B545 melting point
apparatus and are uncorrected. The Mn and PDI values were deter-
mined with a Waters Breeze GPC with HR3 and HR4 columns.
Toluene and THF were used as the standard and the solvent,
respectively.
tone. The substitution of 9 with NBD in 22 regenerates the
active catalyst 25. Alternatively, complex 27 can furnish 29
by transfer hydrogenation (route B). A coordinated NBD
in 29 is inserted into the Ru moiety to form exo-22, which
generates cycloadduct 9, as in route A.
The preliminary study indicated that norbornene deriva-
tives 9 were suitable precursors for ROMP. In the presence
of the Grubbs’ catalyst (30), 9h underwent ROMP to form
polynorbornene 31 in 87% yield (Scheme 5). We deter-
mined the number-averaged molecular weight (Mn) and the
polymer-distribution index (PDI) of this new polymer to be
28.6 kDa and 1.35, respectively.
General Procedure for Preparation of Norbornene Derivatives: A
mixture of the respective diyne (0.30 mmol), [RuCp*Cl2]2
(15.0 µmol), p-xylene (3 mL), NBD (0.5 mL) and iPrOH (0.5 mL)
in a screw-capped Pyrex bottle at ambient temperature was purged
with nitrogen for 5 min. The sealed bottle was heated at 130 °C for
ca. 68 h. After the mixture was cooled to room temperature, the
solvent was removed under reduced pressure, and the residue was
subjected to chromatography on silica gel (or alumina). Elution
with hexane/CH2Cl2 afforded the coupling product.
(5α,5aα,9aα,10α)-5,10-Diphenyl-5,5a,6,9,9a,10-hexahydro-6β,9β-
methanonaphtho[3,2-k]pyracene (7a): Yield: 99.5 mg (74 %) from
12a (105 mg, 0.30 mmol), as a yellow solid, m.p. 256 °C. 1H NMR
(300 MHz, CDCl3): δ = 1.60 (d, 2J = 8.8 Hz, 1 H, CHCH2CH),
2
3
2.12 (d, J = 8.8 Hz, 1 H, CHCH2CH), 2.31 (d, J = 7.4 Hz, 2 H,
5a-H and 9a-H), 2.73 (s, 2 H, 6-H and 9-H), 3.32 (s, 4 H, 1-H and
3
2-H), 3.76 (d, J = 7.4 Hz, 2 H, 5-H and 10-H), 6.05 (s, 2 H, 7-H
Scheme 5. Synthesis of ROMP polymer 31 from norbornene 9h.
3
3
and 8-H), 6.08 (d, J = 6.9 Hz, 2 H, Ar-H), 6.97 (d, J = 6.9 Hz, 2
H, Ar-H), 7.43–7.51 (m, 10 H, Ar-H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 32.0 (C-1 and C-2), 43.8 (CHCH2CH), 46.3 (C-6 and
C-9), 48.6 (C-5 and C-10), 50.6 (C-5a and C-9a), 119.9 (CH), 125.5
(CH), 126.8 (CH), 127.1 (Cquat), 128.3 (CH), 129.7 (CH), 133.7
(Cquat), 134.1 (Cquat), 137.4 (C-7 and C-8), 141.3 (Cquat), 144.7
(Cquat), 145.6 (Cquat) ppm. MS (70 eV): m/z (%) = 448 (84) [M]+,
381 (100) [M – C5H7]+, 305 (97), 292 (68), 276 (42), 226 (24), 152
(25), 91 (54), 77 (37) [C6H5]+. HRMS (EI): calcd. for C35H28
448.2191; found 448.2181.
Conclusions
This work elucidated a simple approach for preparing
new norbornene derivatives 7–11 with high diastereoselec-
tivity from diynes and NBD. One of the cycloadducts was
used to form a new polynorbornene by ROMP. Further
studies of the physical properties of functionalized poly-
mers/copolymers and their applications are in progress.
(5α,5aα,9aα,10α)-5,10-Bis(3,5-dimethylphenyl)-5,5a,6,9,9a,10-hexa-
hydro-6β,9β-methanonaphtho[3,2-k]pyracene (7b): Yield: 76.8 mg
(62%) from 12b (101 mg, 0.25 mmol), as a yellow solid, m.p. 262–
1
2
263 °C. H NMR (300 MHz, CDCl3): δ = 1.58 (d, J = 8.8 Hz, 1
Experimental Section
2
H, CHCH2CH), 2.08 (d, J = 8.8 Hz, 1 H, CHCH2CH), 2.26 (d,
General: 1H and 13C NMR spectra were recorded with a Bruker
300 (300 and 75.5 MHz) spectrometer. The assignments listed in
the 1H and 13C NMR data below were supported by DEPT,
NOESY, and COSY experiments. MS data were recorded with a
Bruker Daltonics Apex II30 spectrometer. X-ray crystal-structure
3J = 7.7 Hz, 2 H, 5a-H and 9a-H), 2.37 (s, 12 H, CH3), 2.74 (s, 2
3
H, 6-H and 9-H), 3.33 (s, 4 H, 1-H and 2-H), 3.65 (d, J = 8.8 Hz,
2 H, 5-H and 10-H), 6.06 (s, 2 H, 7-H and 8-H), 6.13 (d, 3J =
3
7.1 Hz, 2 H, Ar-H), 6.99 (d, J = 7.1 Hz, 2 H, Ar-H), 7.04 (s, 2 H,
Ar-H), 7.11 (s, 4 H, Ar-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ
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Y.-T. Wu et al.
FULL PAPER
= 21.4 (CH3), 32.0 (C-1 and C-2), 43.8 (CHCH2CH), 46.4 (C-6 and
(70 eV): m/z (%) = 556 (90) [M]+, 489 (92), 411 (19), 372 (23), 359
C-9), 48.4 (C-5 and C-10), 50.4 (C-5a and C-9a), 119.9 (CH), 125.5
(100), 346 (51), 330 (17). HRMS (EI): calcd. for C35H22F6
(CH), 127.6 (2 CH), 128.3 (CH), 133.9 (Cquat), 137.4 (C-7 and C- 556.1626; found 556.1616.
8), 137.5 (4 Cquat), 141.4 (Cquat), 144.7 (Cquat), 145.3 (Cquat) ppm.
(7α,7aα,11aα,12α)-1,4-Dimethyl-7,12-diphenyl-7,7a,8,11,11a,12-
MS (70 eV): m/z (%) = 504 (90) [M]+, 438 (100) [M – C5H6]+, 423
(28), 333 (67), 320 (61), 119 (24), 91 (49), 79 (28). HRMS (EI):
calcd. for C39H36 504.2817; found 504.2820.
hexahydro-8β,11β-methanobenzo[e]naphtho[3,2-k]pyracene (8a):
Yield: 84.9 mg (54%) from 16a (129 mg, 0.30 mmol), as a yellow
1
solid, m.p. 291–292 °C. H NMR (300 MHz, CDCl3): δ = 1.56 (d,
2J = 9.1 Hz, 1 H, CHCH2CH), 2.02 (d, 2J = 9.1 Hz, 1 H,
(5α,5aα,9aα,10α)-5,10-Bis(4-tolyl)-5,5a,6,9,9a,10-hexahydro-6β,9β-
methanoacenaphtho[3,2-k]pyracene (7c): Yield: 42.0 mg (34%), from
12c (100 mg, 0.26 mmol), as a yellow solid, m.p. 280–281 °C. 1H
NMR (300 MHz, CDCl3): δ = 1.58 (d, 2J = 8.8 Hz, 1 H,
3
CHCH2CH), 2.17 (d, J = 7.4 Hz, 2 H, 7a-H and 11a-H), 2.26 (s,
3
6 H, CH3), 2.66 (s, 2 H, 8-H and 11-H), 3.47 (d, J = 8.0 Hz, 2 H,
3
7-H and 12-H), 5.40 (d, J = 6.9 Hz, 2 H, Ar-H), 6.01 (s, 2 H, 9-
3
2
3
H and 10-H), 6.62 (s, 2 H, 2-H and 3-H), 6.76 (d, J = 6.9 Hz, 2
CHCH2CH), 2.10 (d, J = 8.8 Hz, 1 H, CHCH2CH), 2.27 (d, J =
H, Ar-H), 7.36–7.44 (m, 10 H, Ar-H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 19.4 (CH3), 43.8 (CHCH2CH), 46.3 (C-8 and C-11),
48.1 (C-7 and C-12), 50.6 (C-7a and C-11a), 123.2 (CH), 125.1
(CH), 126.9 (CH), 128.3 (2 CH), 129.6 (2 CH), 130.4 (CH), 130.9
(Cquat), 132.5 (Cquat), 132.6 (Cquat), 137.4 (C-9 and C-10), 138.7
7.8 Hz, 2 H, 5a-H and 9a-H), 2.49 (s, 6 H, CH3), 2.73 (s, 2 H, 6-
3
H and 9-H), 3.33 (s, 4 H, 1-H and 2-H), 3.71 (d, J = 7.8 Hz, 2 H,
3
5-H and 10-H), 6.06 (s, 2 H, 7-H and 8-H), 6.14 (d, J = 7.0 Hz, 2
3
3
H, Ar-H), 7.00 (d, J = 7.0 Hz, 2 H, Ar-H), 7.27 (d, J = 7.7 Hz,
4 H, Ar-H), 7.40 (d, 3J = 7.7 Hz, 4 H, Ar-H) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 21.3 (CH3), 32.0 (C-1 and C-2), 43.9
(CHCH2CH), 46.3 (C-6 and C-9), 48.1 (C-5 and C-10), 50.6 (C-5a
and C-9a), 119.9 (CH), 125.5 (CH), 127.3 (Cquat), 129.0 (2 CH),
129.2 (Cquat), 129.6 (2 CH), 133.8 (Cquat), 134.3 (Cquat), 136.2
(Cquat), 137.4 (C-7 and C-8), 141.5 (Cquat), 141.7 (Cquat), 145.4
(Cquat) ppm. MS (70 eV): m/z (%) = 476 (100) [M]+, 410 (72) [M –
C5H6]+, 395 (20), 319 (39), 306 (42), 105 (20), 91 (20), 66 (35)
[C5H6]+. HRMS (EI): calcd. for C37H32 476.2504; found 476.2503.
(Cquat), 139.0 (Cquat), 140.6 (Cquat), 143.9 (Cquat), 144.2 (Cquat
)
ppm. MS (70 eV): m/z (%) = 524 (90) [M]+, 458 (33) [M – C5H6]+,
443 (58), 368 (36), 236 (46), 123 (36), 109 (48), 97 (78), 91 (82), 83
(100), 77 (40) [C7H5]+. HRMS (EI): calcd. for C41H32 524.2504;
found 524.2501.
(4α,4aα,8aα,9α)-4,9-Diphenyl-2,3,4,4a,5,8,8a,9-octahydro-1H-
5β,8β-methanocyclopenta[b]naphthalene (9a): Yield: 114 mg (82%)
from 17a (100 mg, 0.41 mmol), as a white solid, m.p. 110–111 °C.
1H NMR (300 MHz, CDCl3): δ = 1.50 (d, 2J = 8.4 Hz, 1 H,
CHCH2CH), 1.68–1.76 (m, 2 H, 2-H), 1.84–1.94 (m, 5 H, 1-H and
3-H), 2.16–2.23 (m, 2 H, 4a-H and 8a-H), 2.60 (s, 2 H, 5-H and 8-
H), 3.08 (br. s, 2 H, 4-H and 9-H), 5.97 (s, 2 H, 6-H and 7-H),
7.22–7.29 (m, 6 H, Ph-H), 7.32–7.39 (m, 4 H, Ph-H) ppm. 13C
NMR (75.5 MHz, CDCl3): δ = 22.3 (C-2), 34.7 (C-1 and C-3), 43.8
(CHCH2CH), 46.8 (C-5 and C-8), 48.8 (C-4 and C-9), 49.4 (C-4a
and C-8a), 126.0 (CH), 128.2 (2 CH), 128.7 (2 CH), 137.1 (C-6
and C-7), 139.3 and 145.3 (C-3a, C-9a, Cquat, and C-Ar) ppm. MS
(70 eV): m/z (%) = 338 (8) [M]+, 272 (100), 243 (22), 165 (26), 115
(24), 91 (48), 66 (43). HRMS (EI): calcd. for C26H26 338.2035;
found 338.2029.
(5α,5aα,9aα,10α)-5,10-Bis(4-fluorophenyl)-5,5a,6,9,9a,10-hexahydro-
6β,9β-methanoacenaphtho[3,2-k]pyracene (7d): Yield: 46.6 mg
(38%) from 12d (100 mg, 0.26 mmol), as a yellow solid, m.p. 278–
1
2
279 °C. H NMR (300 MHz, CDCl3): δ = 1.60 (d, J = 8.7 Hz, 1
2
H, CHCH2CH), 2.07 (d, J = 8.7 Hz, 1 H, CHCH2CH), 2.22 (d,
3J = 7.5 Hz, 2 H, 5a-H and 9a-H), 2.69 (s, 2 H, 6-H and 9-H), 3.34
3
(s, 4 H, 1-H and 2-H), 3.74 (d, J = 7.5 Hz, 2 H, 5-H and 10-H),
6.05 (s, 2 H, 7-H and 8-H), 6.13 (d, J = 7.0 Hz, 2 H, Ar-H), 7.00
(d, J = 7.0 Hz, 2 H, Ar-H), 7.14 (d, J = 8.5 Hz, 2 H, Ar-H), 7.16
3
3
3
3
3
3
(d, J = 8.5 Hz, 2 H, Ar-H), 7.46 (dd, JH,F = 5.6, J = 7.5 Hz, 4
H, Ar-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 32.1 (C-1 and
C-2), 43.8 (CHCH2CH), 46.2 (C-6 and C-9), 47.8 (C-5 and C-10),
50.9 (C-5a and C-9a), 115.1 (CH), 115.4 (CH), 120.0 (CH), 125.6
(CH), 127.3 (Cquat), 130.9 (CH), 131.0 (CH), 133.5 (Cquat), 134.4
(Cquat), 137.4 (C-7 and C-8), 140.4 (Cquat), 141.1 (Cquat), 145.9
(4α,4aα,8aα,9α)-4,9-Bis(4-fluorophenyl)-2,3,4,4a,5,8,8a,9-octahydro-
1H-5β,8β-methanocyclopenta[b]naphthalene (9d): Yield: 33.7 mg
(23%) from 17d (113 mg, 0.40 mmol), as a white solid, m.p. 136–
(Cquat), 162.0 (d, JC,F = 245 Hz, Ar-C, Cquat) ppm. 19F NMR
1
1
2
137 °C. H NMR (300 MHz, CDCl3): δ = 1.48 (d, J = 8.5 Hz, 1
H, CHCH2CH), 1.68–1.77 (m, 2 H, 2-H), 1.83–1.91 (m, 5 H, 1-H
and 3-H), 2.12–2.18 (m, 2 H, 4a-H and 8a-H), 2.55 (s, 2 H, 5-H
(282.4 MHz, CDCl3): δ = –116.5 (s) ppm. MS (70 eV): m/z (%) =
484/485/486/487 (100/37/8/1) [M]+, 418 (71) [M – C5H6]+, 375 (16),
323 (46), 310 (50). HRMS (EI): calcd. for C35H26F2 484.2003;
found 484.1995.
3
and 8-H), 3.04 (d, J = 4.8 Hz, 2 H, 4-H and 9-H), 5.96 (s, 2 H, 6-
3
3
H and 7-H), 7.02 [apparent t (dd), J = 8.5, JH,F = 8.5 Hz, 4 H,
Ar-H], 7.15–7.21 (m, 4 H, Ar-H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 22.3 (C-2), 34.6 (C-1 and C-3), 43.8 (CHCH2CH),
46.7 (C-5 and C-8), 48.0 (C-4 and C-9), 49.6 (C-4a and C-8a), 114.9
(5α,5aα,9aα,10α)-5,10-Bis(3,4,5-trifluorophenyl)-5,5a,6,9,9a,10-
hexahydro-6β,9β-methanoacenaphtho[3,2-k]pyracene (7e): Yield:
64.9 mg (53%), from 12e (102 mg, 0.22 mmol), as a yellow solid,
2
3
(d, JC,F = 21 Hz, CH), 130.0 (d, JC,F = 7.7 Hz, CH), 137.1 (C-6
1
2
m.p. 272–273 °C. H NMR (300 MHz, CDCl3): δ = 1.65 (d, J =
and C-7), 139.3 (Cquat, C-3a, and C-9a), 140.79 (Cquat), 140.80
2
8.9 Hz, 1 H, CHCH2CH), 1.98 (d, J = 8.8 Hz, 1 H, CHCH2CH),
2.14 (d, J = 7.4 Hz, 2 H, 5a-H and 9a-H), 2.68 (s, 2 H, 6-H and
9-H), 3.38 (s, 4 H, 1-H and 2-H), 3.66 (d, J = 7.3 Hz, 2 H, 5-H
1
(Cquat), 161.4 (d, JC,F = 244 Hz, Cquat) ppm. 19 F NMR
3
(282.4 MHz, CDCl3): δ = –117.7 (s) ppm. MS (70 eV): m/z (%) =
374 (9) [M]+, 308 (100), 280 (17), 199 (20), 183 (15), 109 (32), 84
(66), 57 (16). HRMS (EI): calcd. for C26H24F2 374.1846; found
374.1835.
3
3
and 10-H), 6.08 (s, 2 H, 7-H and 8-H), 6.28 (d, J = 7.0 Hz, 2 H,
Ar-H), 7.08–7.16 (m, 6 H, Ar-H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 32.2 (C-1 and C-2), 43.8 (CHCH2CH), 46.1 (C-6 and
2
C-9), 48.0 (C-5 and C-10), 50.6 (C-5a and C-9a), 113.4 (dd, JC,F
= 14.3, JC,F = 6.2 Hz, CH), 120.3 and 125.6 (C-3, C-4, C-11, and
(4α,4aα,8aα,9α)-4,9-Bis(3,4,5-trifluorophenyl)-2,3,4,4a,5,8,8a,9-octa-
hydro-1H-5β,8β-methanocyclopenta[b]naphthalene (9e): Yield:
66.0 mg (59%) from 17e (88.0 mg, 0.25 mmol), as colorless crystals
3
C-12), 127.1 (m, Cquat), 132.6 (m, Cquat), 134.6 (m, Cquat), 137.2
(C-7 and C-8), 139.7 (m, Cquat), 140.8 (m, Cquat), 151.1 (ddd, 3JC,F (from CH2Cl2/MeOH), m.p. 160–161 °C. 1H NMR (300 MHz,
2
1
2
= 3.8, JC,F = 9.2, JC,F = 249 Hz, Cquat) ppm. One Cquat cannot
be observed due to signals overlap. 19F NMR (282.4 MHz, CDCl3):
δ = –134.2 (dd, J = 8.5, 19.8 Hz, 2 F), –162.6 (m, 1 F) ppm. MS
CDCl3): δ = 1.52 (d, J = 8.8 Hz, 1 H, CHCH2CH), 1.73–1.86 (m,
5 H, H1, 2-H, and 3-H), 1.88–1.92 (m, 2 H, 1-H and 3-H), 2.03–
2.20 (m, 2 H, 4a-H and 8a-H), 2.53 (s, 2 H, 5-H and 8-H), 2.95
676
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 672–679

Ruthenium-Catalyzed Cascade Reactions of Diynes with Norbornadiene
(br. s, 2 H, 4-H and 9-H), 5.98 (s, 2 H, 6-H and 7-H), 6.82 (dd,
(4α,4aα,8aα,9α)-4,9-Bis(4-anisyl)-1,3,4,4a,5,8,8a,9-octahydro-5β,8β-
4JH,F = 7.1, 3JH,F = 7.4 Hz, 4 H, Ar-H) ppm. 13C NMR (75.5 MHz, methanonaphtho[2,3-c]furane (10k): Yield: 32.6 mg (21%), from 18k
1
CDCl3): δ = 22.2 (C-2), 34.4 (C-1 and C-3), 43.9 (CHCH2CH),
(117 mg, 0.38 mmol), as a white solid, m.p. 214–215 °C. H NMR
46.6 (C-5 and C-8), 48.3 (C-4 and C-9), 49.2 (C-4a and C-8a), 112.4 (300 MHz, CDCl3): δ = 1.52 (d, 2J = 8.8 Hz, 1 H, CHCH2CH),
3
2
2
2
(dd, JC,F = 5.9, JC,F = 14.1 Hz, CH), 137.0 (C-6 and C-7), 138.2
1.83 (d, J = 8.8 Hz, 1 H, CHCH2CH), 1.89 (d, J = 6.6 Hz, 2 H,
4a-H and 8a-H), 2.61 (s, 2 H, 5-H and 8-H), 3.03 (d, J = 6.6 Hz,
2 H, 4-H and 9-H), 3.83 (s, 6 H, OCH3), 4.21–4.25 (m, 2 H, 1-H
1
3
(dm, JC,F = 250 Hz, Cquat), 138.8 (9a, C-3a), 141.1 (m, Cquat),
3
2
1
151.1 (ddd, JC,F = 4.0, JC,F = 9.9, JC,F = 250 Hz, Cquat) ppm.
19F NMR (282.4 MHz, CDCl3): δ = –134.9 (dd, J = 11.3, 19.7 Hz, and 3-H), 4.46–4.50 (m, 2 H, 1-H and 3-H), 5.96 (s, 2 H, 6-H and
2 F), –163.8 (m, 1 F) ppm. MS (70 eV): m/z (%) = 446 (14) [M]+,
7-H), 6.87 (d, J = 8.5 Hz, 4 H, Ar-H), 7.15 (d, J = 8.5 Hz, 4 H,
3
3
380 (53), 351 (11), 235 (23), 221 (16), 219 (18), 201 (15), 195 (13),
Ar-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 43.9 (CHCH2CH),
169 (16), 145 (27), 91 (17). HRMS (EI): calcd. for C26H20F6 45.3 (C-5 and C-8), 46.5 (C-4 and C-9), 49.9 (C-4a and C-8a), 55.2
446.1469; found 446.1472.
(OCH3), 77.9 (C-1 and C-3), 113.8 (2 CH), 129.3 (2 CH), 135.7
and 136.4 (Cquat, C-3a, C-9a, and C-Ar), 137.1 (C-6 and C-7), 158.3
(Cquat) ppm. MS (70 eV): m/z (%) = 400 (27) [M]+, 334 (61) [M –
C5H6]+, 303 (29), 273 (29), 226 (22), 165 (30), 152 (29), 145 (25),
128 (21), 121 (100), 115 (40), 107 (31), 91 (45), 77 (32). HRMS
(EI): calcd. for C27H28O3 400.2038; found 400.2039.
(4α,4aα,8aα,9α)-4,9-Bis[4-(methoxycarbonyl)phenyl]-2,3,4,4a,5,
8,8a,9-octahydro-1H-5β,8β-methanocyclopenta[b]naphthalene (9g):
Yield: 66.3 mg (52%) from 17g (102 mg, 0.28 mmol), as a white
1
solid, m.p. 158–159 °C. H NMR (300 MHz, CDCl3): δ = 1.50 (d,
2J = 8.8 Hz, 1 H, CHCH2CH), 1.68–1.75 (m, 2 H, 2-H), 1.84–1.90
(m, 5 H, 1-H and 3-H), 2.11–2.19 (m, 2 H, 4a-H and 8a-H), 2.54 (4α,4aα,8aα,9α)-2,2-Bis(methoxycarbonyl)-4,9-bis(3,4,5-trifluoro-
(s, 2 H, 5-H and 8-H), 3.12 (d, 3J = 4.6 Hz, 2 H, 4-H and 9-H),
3.92 (s, 6 H, OCH3), 5.93 (s, 2 H, 6-H and 7-H), 7.29 (d, 3J =
8.3 Hz, 4 H, Ar-H), 8.02 (d, 3J = 8.3 Hz, 4 H, Ar-H) ppm. 13C
phenyl)-1,3,4,4a,5,8,8a,9-octahydro-5β,8β-methanocyclopenta[b]-
naphthalene (11e): Yield: 89.5 mg (62 %) from 19e (121 mg,
0.26 mmol), as a white solid, m.p. 203–205 °C. 1H NMR
NMR (75.5 MHz, CDCl3): δ = 22.3 (C-2), 34.5 (C-1 and C-3), 43.9 (300 MHz, CDCl3): δ = 1.56 (d, 2J = 9.1 Hz, 1 H, CHCH2CH),
2
3
(CHCH2CH), 46.7 (C-5 and C-8), 48.8 (C-4 and C-9), 49.3 (C-4a 1.71 (d, J = 9.1 Hz, 1 H, CHCH2CH), 1.77 (d, J = 6.9 Hz, 2 H,
and C-8a), 52.0 (CO2CH3), 128.2 (Cquat), 128.8 (2 CH), 129.7 (2
CH), 137.0 (C-6 and C-7), 138.9 and 150.6 (Cquat, C-3a, C-9a, and
2
4a-H and 8a-H), 2.54 (s, 2 H, 5-H and 8-H), 2.57 (d, J = 16.2 Hz,
2
2 H, 1-H and 3-H), 2.81 (d, J = 16.2 Hz, 2 H, 1-H and 3-H), 2.95
3
C-Ar), 167.2 (Cquat, CO2CH3) ppm. MS (70 eV): m/z (%) = 454 (7) (d, J = 6.9 Hz, 2 H, 4-H and 9-H), 3.65 (s, 3 H, CO2CH3), 3.72
[M]+, 423 (6) [M – OCH3]+, 388 (100) [M – C5H6]+, 329 (23), 305
(14), 239 (12), 105 (23). HRMS (EI): calcd. for C30H30O4 454.2144;
found 454.2142.
(s, 3 H, CO2CH3), 5.97 (s, 2 H, 6-H and 7-H), 6.80–6.85 (m, 4 H,
Ar-H) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 42.0 (C-1 and C-
3), 43.9 (CHCH2CH), 46.5 (C-5 and C-8), 47.6 (C-4 and C-9), 49.1
(C-4a and C-8a), 52.8 (CO2CH3), 52.9 (CO2CH3), 58.0 (C-2), 112.5
(4α,4aα,8aα,9α)-4,9-Bis(4-trifluoromethylphenyl)-2,3,4,4a,5,8,8a,9-
octahydro-1H-5β,8β-methanocyclopenta[b]naphthalene (9h): Yield:
53.1 mg (42%) from 17h (101 mg, 0.27 mmol), as colorless crystals
(from CH2Cl2/MeOH), m.p. 171–172 °C. 1H NMR (300 MHz,
2
3
(dd, JC,F = 14.4, JC,F = 6.3 Hz, CH), 136.1 (C-3a and C-9a),
1
136.9 (C-6 and C-7), 140.1 (m, Cquat), 151.2 (dm, JC,F = 254 Hz,
Cquat), 172.0 (CO2CH3), 172.1 (CO2CH3) ppm. 19F NMR
(282.4 MHz, CDCl3): δ = –134.2 (dd, J = 5.6, 19.7 Hz, 2 F), –163.2
(m, 1 F) ppm. MS (70 eV): m/z (%) = 562 (4) [M]+, 436 (48), 377
(60), 375 (22), 362 (14), 318 (10), 245 (13), 219 (17), 167 (21), 149
(80), 145 (51), 66 (100), 57 (29). HRMS (EI): calcd. for C30H24F6O4
562.1579; found 562.1573.
2
CDCl3): δ = 1.52 (d, J = 8.8 Hz, 1 H, CHCH2CH), 1.68–1.78 (m,
2 H, 2-H), 1.85–1.90 (m, 5 H, 1-H and 3-H), 2.11–2.18 (m, 2 H,
3
4a-H and 8a-H), 2.55 (s, 2 H, 5-H and 8-H), 3.13 (d, J = 4.7 Hz,
2 H, 4-H and 9-H), 5.95 (s, 2 H, 6-H and 7-H), 7.34 (d, 3J = 7.8 Hz,
4 H, Ar-H), 7.60 (d, 3J = 7.8 Hz, 4 H, Ar-H) ppm. 13C NMR
(75.5 MHz, CDCl3): δ = 22.3 (C-2), 34.5 (C-1 and C-3), 43.9 4-[4,5-Dimethyl-2-(2-thiophenylethynyl)phenyl]-3-(2-thiophenyl)tri-
(CHCH2CH), 46.6 (C-5 and C-8), 48.7 (C-4 and C-9), 49.4 (C-4a cyclo[4.2.1.02,5]nona-3,7-diene (21): Yield: 68.9 mg (56%) from
and C-8a), 124.3 (q, 1JC,F = 272 Hz, CF3), 125.2 (q, 3JC,F = 3.8 Hz,
4,5-dimethyl-1,2-bis(2-thiophenylethynyl)benzene
(100 mg,
2
CH), 128.5 (q, JC,F = 32.3 Hz, Cquat), 129.1 (CH), 137.1 (C-6 and
0.31 mmol), as a white solid. 1H NMR (300 MHz, CDCl3): δ =
C-7), 139.0 (C-3a and C-9a), 149.2 (Cquat) ppm. 19F NMR 1.36 (d, J = 9.2 Hz, 1 H, 9-H), 1.70 (d, 2J = 9.2 Hz, 1 H, 9-H),
2
(282.4 MHz, CDCl3): δ = –62.3 (s) ppm. MS (70 eV): m/z (%) =
2.28 (s, 3 H, CH3), 2.29 (s, 3 H, CH3), 2.67 (s, 2 H, 1-H and 6-H),
3
474 (1) [M]+, 408 (21), 159 (15), 127 (12), 91 (16), 66 (100). HRMS 2.84 (s, 1 H, 2-H or 5-H), 3.11 (d, J = 3.4 Hz, 1 H, 2-H or 5-H),
3
(EI): calcd. for C28H24F6 474.1782; found 474.1792.
6.20–6.24 (m, 2 H, 7-H and 8-H), 6.94 (dd, J = 4.9, 5.0 Hz, 1 H,
Ar-H), 6.97–7.02 (m, 2 H, Ar-H), 7.16–7.22 (m, 3 H, Ar-H), 7.35
(s, 1 H, Ar-H), 7.47 (s, 1 H, Ar-H) ppm. 13C NMR (75.5 MHz,
CDCl3): δ = 19.4 (CH3), 19.7 (CH3), 39.4 and 39.9 (C-2 and C-5),
40.3 (C-9), 44.0 and 46.1 (C-1 and C-6), 85.7 and 93.7 (CϵC),
118.2 (Cquat), 123.6 (Cquat), 124.8 (CH), 125.4 (CH), 126.7 (CH),
126.9 (CH), 127.1 (CH), 129.0 (CH), 131.1 (CH), 133.7 (CH), 134.8
(Cquat), 135.8 (CH), 136.1 (Cquat), 136.2 (CH), 137.2 (Cquat), 138.2
(Cquat), 138.7 (Cquat) ppm. One Cquat could not be observed due to
signal overlap. MS (70 eV): m/z (%) = 410 (100) [M]+, 395 (32) [M –
CH3]+, 362 (16), 344 (24) [M – C5H6]+, 329 (18), 318 (23), 311 (24),
295 (15), 135 (15), 108 (19), 97 (26). HRMS (EI): calcd. for
C27H22S2 410.1163; found 410.1177. Note that 21 decomposes to
4,5-dimethyl-1,2-bis(2-thiophenylethynyl)benzene upon incubation
at room temperature for a few weeks.
(4α,4aα,8aα,9α)-4,9-Bis(4-anisyl)-2,3,4,4a,5,8,8a,9-octahydro-1H-
5β,8β-methanocyclopenta[b]naphthalene (9k): Yield: 67.0 mg (51%)
from 17k (100 mg, 0.33 mmol), as a white solid, m.p. 200–201 °C.
1H NMR (300 MHz, CDCl3): δ = 1.45 (d, 2J = 8.4 Hz, 1 H,
CHCH2CH), 1.63–1.72 (m, 2 H, 2-H), 1.81–1.88 (m, 5 H, 1-H and
3-H), 2.11–2.17 (m, 2 H, 4a-H and 8a-H), 2.55 (s, 2 H, 5-H and 8-
3
H), 2.99 (d, J = 4.7 Hz, 2 H, 4-H and 9-H), 3.82 (s, 6 H, OCH3),
3
5.95 (s, 2 H, 6-H and 7-H), 6.87 (d, J = 8.5 Hz, 4 H, Ar-H), 7.13
3
(d, J = 8.5 Hz, 4 H, Ar-H) ppm. 13C NMR (75.5 MHz, CDCl3):
δ = 22.3 (C-2), 34.7 (C-1 and C-3), 43.8 (CHCH2CH), 46.8 (C-5
and C-8), 47.9 (C-4 and C-9), 49.6 (C-4a and C-8a), 55.2 (OCH3),
113.5 (2 CH), 129.7 (2 CH), 137.1 (C-6 and C-7), 137.5 and 139.4
(Cquat, C-3a, C-9a, and C-Ar), 157.9 (Cquat) ppm. MS (70 eV): m/z
(%) = 398 (26) [M]+, 332 (96) [M – C5H6]+, 224 (24), 211 (32), 166
(23), 121 (100), 91 (32), 84 (46), 81 (62), 71 (35). HRMS (EI): calcd. Ring-Opening Metathesis Polymerization of 9h: A solution of nor-
for C28H30O2 398.2246; found 398.2248.
bornene 9h (71.0 mg, 0.15 mmol) in CH2Cl2 (4 mL) was treated
Eur. J. Org. Chem. 2010, 672–679
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
677

Y.-T. Wu et al.
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with the Grubbs’ catalyst 30 (25.0 mg, 20.0 µmol), and the reaction
mixture was heated at 40 °C under nitrogen for 30 min. Ethyl vinyl
ether (0.5 mL) was added to the solution, and the mixture was
stirred at the same temperature for 15 min. After cooling to room
temperature, the solvent was removed under reduced pressure, and
the residue was washed with MeOH to afford polynorbornene 31
(62.0 mg, 87%) as an off-white solid.
Supporting Information (see footnote on the first page of this arti-
cle): Procedures for the preparation of the diynes and their analytic
data.
[9]
Acknowledgments
This work was supported by the National Science Council of Tai-
wan (NSC96-2113-M-006-008-MY2). We also thank Prof. S.-L.
Wang and Ms. P.-L. Chen (National Tsing-Hua University, Taiwan)
for the X-ray structure analyses.
[1] a) H. K. Hall, C. D. Smith, J. H. Baldt, J. Am. Chem. Soc.
1973, 95, 3197–3201; the strain energy of norbornene was also
reported as 27.2 kcal/mol; see: b) T. H. Lowry, K. S. Richard-
son, Mechanism and Theory in Organic Chemistry, 3rd ed.,
Harper Collins, New York, 1987; c) P. R. Khoury, J. D. God-
dard, W. Tam, Tetrahedron 2004, 60, 8103–8112; d) J. Howell,
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The reaction of 8H-cyclopent[a]acenaphthylen-8-ones with
NBD gives fluoranthenes with the loss of CO and cyclopenta-
diene. Formally, NBD can be regarded as a pre-acetylene; see:
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[13]
[14]
3
The coupling constant ( J = 7.4 Hz) for 5-H/5a-H and 10-H/
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For reviews, see: a) S. Gladiali, E. Alberico, Chem. Soc. Rev.
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[8] Selected examples: a) R. R. Burton, W. Tam, J. Org. Chem.
2007, 72, 7333–7336; b) R. W. Jordan, K. Villeneuve, W. Tam,
J. Org. Chem. 2006, 71, 5830–5833; c) N. Riddell, W. Tam, J.
Org. Chem. 2006, 71, 1934–1937; d) T. Shibata, K. Takami,
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678
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 672–679

Ruthenium-Catalyzed Cascade Reactions of Diynes with Norbornadiene
[18] a) T. S. Chou, S. C. Hung, J. Org. Chem. 1988, 53, 3020–3027;
b) E. Briard, J. Levillain, J.-L. Ripoll, Y. Dat, A. Marcual, C.
Lange, Phosphorus, Sulfur Silicon Relat. Elem. 2000, 165, 135–
148.
[19] For a metal-catalyzed cycloaddition of 1,3-butadienes with
NBD, see: a) B. Ma, J. K. Snyder, Org. Lett. 2002, 4, 2731–
2734; b) B. Ma, J. K. Snyder, Organometallics 2002, 21, 4688–
4695; c) Y. Chen, R. Kiattansakul, B. Ma, J. K. Snyder, J. Org.
Compound 9h: C26H20F6, triclinic crystals of space group P1,
unit-cell dimensions: a = 6.8236(3), b = 7.4049(3), c =
36.375(6) Å, α = 102.834(3), β = 107.013(3), γ = 91.727(3)°,
V = 504.71(4) Å3, Z = 1, crystal size: 0.12ϫ0.10ϫ0.10 mm.
CCDC-746967 (for 9e) and -746968 (for 9h) contain the supple-
mentary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Chem. 2001, 66, 6932–6942.
[24]
It was reported that in the presence of ethanol and NBD, the
[RuCl2Cp*]2 complex can be easily reduced to form the active
catalyst [RuCl(η4-NBD)Cp*]; see ref.[13]
[20] R. G. Compton, A. C. Fisher, R. G. Wellington, J. Winkler, D.
Bethell, P. Lederer, J. Chem. Soc. Perkin Trans. 2 1992, 1359–
1362.
[25]
[26]
The exo stereoselectivity for [2+2] cycloadditions of NBD with
[21] a) R. M. Beesley, C. K. Ingold, J. F. Thorpe, J. Chem. Soc.
1915, 107, 1080–1106; b) C. K. Ingold, J. Chem. Soc. 1921, 119,
305–329; c) C. K. Ingold, S. Sako, J. F. Thorpe, J. Chem. Soc.
1922, 1177–1198; d) G. Hammond in Steric Effects in Organic
Chemistry (Ed.:M. S. Newman), Wiley, New York, 1956, p.
462.
alkynes has also been obtained previously; for details, see ref.[8]
The study of the stereoselectivity of Ni-catalyzed [2+2] cyclo-
additions of NBD with N-phenylmaleimide indicates that the
exo adduct predominated at higher temperature (110 °C); see:
M. Lautens, L. G. Edwards, W. Tam, A. J. Lough, J. Am.
Chem. Soc. 1995, 117, 10276–10291.
Cycloadducts generated by a cobalt-catalyzed [(2+2)+2] cyclo-
addition of 1,6-heptadiynes with norbornene and benzonor-
bornadiene can be isolated; see: M.-S. Wu, D. K. Rayabarapu,
C.-H. Cheng, Tetrahedron 2004, 60, 10005–10009.
Received: September 10, 2009
[22] Caution: The reaction of catalyst [RuCl2Cp*]2 with neat dipro-
pargyl ether under aerobic conditions could cause ignition.
[23] Crystals of 9e and 9h were grown from CH2Cl2/MeOH. Com-
pound 9e: C28H24F6, triclinic crystals of space group P1, unit-
[27]
cell dimensions:
a = 9.0375(10), b = 10.8019(12), c =
12.8635(14) Å, α = 74.999(2), β = 72.041(2), γ = 72.324(2)°,
V = 1119.1(2) Å3, Z = 2, crystal size: 0.45ϫ0.45ϫ0.15 mm.
Published Online: December 8, 2009
Eur. J. Org. Chem. 2010, 672–679
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
679