Rhodium(I)-catalyzed intramolecular carbonylative [2+2+1] cycloadditions and cycloisomerizations of bis(sulfonylallene)s

Article abstract of DOI:10.1002/chem.200903568

Novel [{RhCl(CO)dppp}₂]catalyzed intramolecular carbonylative [2+2+1] cycloadditions of bis(phenylsulfonylallene) derivatives under CO, leading to the facile formation of bis(phenylsulfonyl)bicyclo[n.3.0] frameworks (n=4-6), have been developed. The terminal double bonds of both allenyl moieties served exclusively as the two π-components. In particular, this newly developed method was shown to be a powerful tool for the construction of bicyclo[6.3.0]undecadienones, which have hardly been prepared by the known Pauson-Khand (-type) reac-tions. The bicyclo[7.3.0]dodecadienone homologue (one extra carbon) could be formed in rather low yields. Alternatively, novel cycloisomerizations of bis(phenylsulfonylallene) derivatives with catalysis by the same Rh¹ complex under N₂ readily produced the 3,4-dimethylene-2,5-bis(phenylsulfonyl)cyclononene and the corresponding cyclooctene and cycloheptene frameworks.

Full text of DOI:10.1002/chem.200903568

FULL PAPER
DOI: 10.1002/chem.200903568
Rhodium(I)-Catalyzed Intramolecular Carbonylative [2+2+1]
Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
Takamasa Kawamura, Fuyuhiko Inagaki, Syu Narita, Yasuhito Takahashi, Shuichi Hirata,
Shinji Kitagaki, and Chisato Mukai*[a]
Abstract: Novel [{RhCl(CO)dppp}2]-
catalyzed intramolecular carbonylative
[2+2+1] cycloadditions of bis(phenyl-
sulfonylallene) derivatives under CO,
leading to the facile formation of
newly developed method was shown to
be a powerful tool for the construction
of bicycloACTHNUTRGNEUNG[6.3.0]undecadienones, which
have hardly been prepared by the
known Pauson–Khand (-type) reac-
tions. The bicycloACTHNGUTERNNU[G 7.3.0]dodecadienone
homologue (one extra carbon) could
be formed in rather low yields. Alter-
natively, novel cycloisomerizations of
bis(phenylsulfonylallene)
derivatives
bis(phenylsulfonyl)bicyclo
N
with catalysis by the same RhI complex
under N2 readily produced the 3,4-di-
methylene-2,5-bis(phenylsulfonyl)cyclo-
works (n=4–6), have been developed.
The terminal double bonds of both al-
lenyl moieties served exclusively as the
two p-components. In particular, this
Keywords: allenes · cycloaddition ·
cycloisomerization
· medium-ring
AHCTUNGTRENNUNG
compounds · rhodium
AHCTUNGTRENNUNG
Introduction
1-phenylhepta-1,6-diene into the bicyclo
ACHTUNGTREN[NGNU 3.3.0] compound
via zirconacyclopentane derivative was reported
a
The Co2(CO)8-mediated [2+2+1] cycloaddition of three
components—an alkyne p-bond, an alkene p-bond, and
carbon monoxide (CO)—is known as the Pauson–Khand re-
action,[1] and its intramolecular version provides both the
most straightforward and the most powerful methodology
for the construction of cyclopentenone-fused bicyclic frame-
works (Scheme 1, conversion of 1 into 2). Several transition
metals, such as Rh, Ir, Mo, Zr, Ti, and so on, have now been
found to be useful catalysts for carbonylative [2+2+1] cyclo-
additions of this type.[2] These ring-closing reactions have
been limited almost exclusively to the use of alkyne p-bonds
as one of the two p-bond components, although there have
been several reported Pauson–Khand-type [2+2+1] cycload-
ditions based on an alternative p-component instead of the
alkyne p-bond. The stepwise stoichiometric conversion of
(Scheme 1, conversion of 3 into 4, R=Ph).[3] Wender[4] de-
veloped [{RhCl(CO)2}2]-catalyzed [2+2+1] cycloadditions of
1,3-dienes, alkenes, and CO, in which the 1,3-diene moiety
served as the alkene p-bond[5] instead of the alkyne p-com-
ponent (Scheme 1, conversion of 3 into 4, R=vinyl). Itoh
described an example of [{RhCl(CO)2}2]-catalyzed [2+2+1]
cycloaddition between the internal double bond of the allen-
yl moiety and a vinylsilane (Scheme 1, conversion of 5 into
6).[6] We have also developed a new procedure[7] for the for-
mation of bicycloACTHNUGTRENNUG[5.3.0] and bicycloACHUTNGTREN[NGUN 4.3.0] ring systems
based on [{RhCl(CO)2}2]-catalyzed [2+2+1] cycloadditions
of the terminal double bond of an allene and an alkene
(Scheme 1, conversion of 5 into 7).
[a] T. Kawamura, Dr. F. Inagaki, S. Narita, Y. Takahashi, S. Hirata,
Dr. S. Kitagaki, Prof. Dr. C. Mukai
Division of Pharmaceutical Sciences
Graduate School of Natural Science and Technology
Kanazawa University
Kakuma-machi, Kanazawa 920-1192 (Japan)
Fax : (+81)76-234-4410
E-mail: cmukai@kenroku.kanazawa-u.ac.jp
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.200903568.
Scheme 1. Intramolecular carbonylative [2+2+1] cycloadditions of two
p-components and CO.
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5173

On the other hand, the synthetic versatility of bis
G
of a RhI-catalyzed carbonylative [2+2+1] cycloaddition of a
bis(allene) focused on the preparation of a bicyclo[5.3.0]-
decadienone from the bis(phenylsulfonylallene) compound
8a.
A solution of 8a in toluene was thus heated at 808C
under CO in the presence of [{RhCl(CO)dppp}2] (5 mol%)
has recently been demonstrated by the Ma group,[8–11] who
G
ACHTUNGTRENNUNG
have found that the thermal and Pd-catalyzed [2+2] cyclo-
E
ACHTUNGTRENNUNG
additions of 1,5-bis
mation of bicyclo[5.2.0] and bicyclo
spectively.[8] Interestingly, they also disclosed that 1,5-bis-
(allene)s underwent bimolecular cyclization to afford ste-
roid-like skeletons with the aid of trans-[RhCl(CO)-
(PPh3)2],[9] whereas 1,5-bis
(allene) derivatives with
ACHTUNGTRENNUNG
A
U
A
for 1 h to afford 2,6-bis(phenylsulfonyl)bicycloACTHNGUTERNN[UG 5.3.0]deca-
1,7-dien-9-one (9a) in quantitative yield (Table 1, entry 1).
The formation of 9a can be interpreted in terms of the inter-
mediacy of the initially formed 1,3-diene derivative 9a’ and
its subsequent isomerization to the a,b-unsaturated ketone
9a. The alternative catalyst [{RhCl(CO)2}2] also gave the
ring-closing products 9a in 85% yield, although a longer re-
action time (6 h) was necessary (Table 1, entry 2). Increasing
the amount of [{RhCl(CO)2}2] from 5 to 10 mol% provided
9a in a better yield and in a shorter reaction time (Table 1,
entry 3). It should be mentioned that a rather lower reaction
temperature (808C) than in the cases of allenynes and al-
C
ACHTUNGTRENNUNG
substituents at the allenic terminus gave seven-membered
cross-conjugated trienes through cycloisomerization when
treated with [{RhCl(CO)2}2].[10] Chung and Kang also re-
ported intriguing cycloisomerizations and carbonylative
[2+2+1] cycloadditions of 1,5-bis
interest in the fields of
[{RhCl(CO)dppp}2]-catalyzed allenic
(allene)s.[12] Our contiguous
ACHTUNGTRENNUNG
[{RhCl(CO)2}2]-
cycloadditions[7,13]
prompted us to investigate carbonylative [2+2+1] cycloaddi-
tions between two allenic p-bonds. We also investigated cy-
cloisomerizations of the bis
N
lenenes, which required toluene or xylene at reflux,[7,13] was
ACHTUNGTRENNUNG
sufficient to complete this ring-closing reaction. No [2+2]
cycloaddition products could be detected under either set of
reaction conditions, presumably because of the low reaction
temperature.[20]
The malonate derivative 8b in the presence of
[{RhCl(CO)dppp}2] (5 mol%), however, unexpectedly fur-
ACHTUNGTRENNUNGallene)s to effect the easy preparation of medium-sized
bicycloACHTUNGTRENNUNG[n.3.0] skeletons and monocyclic rings containing two
vicinal exo-methylene moieties, respectively.[14]
Results and Discussion
Table 1. Rhodium(I)-catalyzed synthesis of bicyclo
ditions of bis
(allene)s.[a]
ACHTUNGTREN[NUGN 5.3.0] compounds through carbonylative [2+2+1] cycload-
AHCTUNGTRENNUNG
Rhodium(I)-catalyzed intramo-
lecular carbonylative [2+2+1]
cycloadditions of bis(sulfonylal-
lene)s: Intramolecular Pauson–
Khand reactions of enynes
(alkyne/alkene derivatives) can
generally be applied to the for-
Entry Bis
(allene)
RhI catalyst
[{RhCl(CO)dppp}2]
[{RhCl(CO)2}2]
[{RhCl(CO)2}2][c]
t [h]
Products (yield)[b]
mation of bicyclo
nones and bicyclo[4.3.0]none-
ACHTUNGTRENNUNGnones in good to high yields.
ACHTUNGTREN[NUNG 3.3.0]octe-
1
2
3
G
1
6
3
AHCTUNGTRENNUNG
A
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
However, the application of
this protocol to the construction
4
5
6
7
N
2
2
1
1
of larger-sized bicycloCAHTUNGTRENUN[NG 5.3.0]-
A
ACHTUNGTRENNUNG
achieved except in the cases of
a few specific substrates, pos-
sessing, for example, an aromat-
ic ring as the template.[15]
8
9
1
3
RhI-catalyzed
carbonylACTHNGUTERNNUaG tive
[2+2+1] cycloadditions[16] of al-
lenynes (alkyne/allene deriva-
tives)[13,17,18] or allenenes (al-
10
11
12
0.5
20
4
ACHTUNGTRENNUNG
kene/allene)[7] has, however,
been reported, by ourselves[7,13]
and by Brummond et al.,[17] to
afford the corresponding biACTHNUTRGNEUGcN y-
ACHTUNGTRENNUNGcloACHTUNGTRENNUNG[5.3.0] compounds in satis-
[a] Reaction conditions: a solution of the bis
(1 mL) was stirred under CO at 808C. [b] Yields of isolated products. [c] 10 mol% of the catalyst. Ts=p-tolu-
enesulfonyl; dppp=1,3-bis(diphenylphosphino)propane.
(allene) 8 (0.1 mmol) and the RhI catalyst (5 mol%) in toluene
ACHTUNGTRENNUNG
factory yields.[19] On these
grounds, our initial evaluation
N
ACHTUNGTRENNUNG
5174
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 5173 – 5183

Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
FULL PAPER
nished 9b only in low yield, along with the predominant
[2+2] cycloaddition product 10b in 70% yield (Table 1,
entry 4). An increase in the amount of [{RhCl(CO)dppp}2]
used did not improve the yield of 9b (Table 1, entry 5). Al-
though the rhodium catalyst had not necessarily been essen-
tial for the production of 10b, it might have accelerated the
[2+2] cycloaddition reaction, probably through the interme-
diacy of a rhodacycle (vide infra).[21,22] Indeed, when 8b was
heated in toluene in the absence of catalyst at 808C for 6 h,
10b was obtained in 98% yield. Satisfactory yields (83 or
89%) of 9b were achieved through the use of
[{RhCl(CO)2}2] in place of [{RhCl(CO)dppp}2] (Table 1, en-
tries 6 and 7).
The substrate 8c, containing a nitrogen atom, reacted in
the presence of [{RhCl(CO)dppp}2] to afford the corre-
sponding azabicycloACTHNUGRTENUNG[5.3.0]decadienone 9c in 98% yield
(Table 1, entry 8). When 8c was treated with
[{RhCl(CO)2}2], however, 9c was formed only in a low yield
(44%) and the [2+2] cycloaddition product 10c was ob-
tained as a by-product (Table 1, entry 9).
Scheme 2. Intramolecular carbonylative [2+2+1] cycloadditions of mono-
The oxa congener 9d could also be synthesized in a satis-
factory yield from 8d in the presence of [{RhCl(CO)dppp}2]
(Table 1, entry 10). Again, [{RhCl(CO)2}2] provided 9d in a
rather low yield (Table 1, entries 11 and 12). The results in
Table 1 therefore indicate that [{RhCl(CO)dppp}2] is superi-
or to [{RhCl(CO)2}2] for carbonylative [2+2+1] cycloaddi-
or non-sulfonylated bisACTHNUGRTENUNG(allene)s.
tions of the bisACHTUNGTRENNUNG(allene) derivatives 8, except in the case of
the malonate derivative 8b (Table 1, entries 4–7).
The mono-phenylsulfonyl derivative 8e (Scheme 2), upon
treatment with [{RhCl(CO)dppp}2] (5 mol%), also produced
the corresponding bicycloACTHNUTRGENUGN[5.3.0] derivative 9ea in 45%
yield. An increase in the amount of the catalyst used led to
an increase in the total yield of the [2+2+1] cycloadducts
(63%), this time including the isomer 9eb.[23] The malonate
derivative 8 f (Scheme 2) underwent the ring-closing reac-
tion to produce the two carbonylative [2+2+1] cycloaddi-
tion products 9 f and 11, each in 15% yield, along with the
[2+2] cycloaddition product 10 f (14% yield). The bicyclo-
Scheme 3. Formation and reactions of rhodacycle intermediates from bis-
AHCTUNGTRENNG(UN allene)s A.
ACHTUNGTRENNUNG[4.3.0] derivative 11, containing the exomethylene moiety,
must have been obtained through the reaction between the
terminal and internal double bonds of the two allenyl
groups. This observation differs from those mentioned previ-
ously, in which the ring-closing reactions consistently in-
volved the participation of the two terminal double bonds of
the allenyl functionalities. Furthermore, the non-sulfonylat-
ed derivative 8g (Scheme 2) provided only intractable mix-
tures under several sets of conditions.
These results, in combination with those shown in Table 1,
imply that the introduction of two phenylsulfonyl groups on
the two allenyl functionalities makes intramolecular carbon-
ylative [2+2+1] cycloadditions between the terminal double
bonds of the two allenyl groups extremely smooth
(Scheme 3, A!B!C). The bulky phenylsulfonyl groups
might not only suppress cyclometallation between the two
internal double bonds (Scheme 3, A!E)[8] or between one
terminal and one internal double bond of two allenyl groups
(Scheme 3, A!F),[9] but might also orient the two terminal
double bonds of the allenyl moieties such that they can
react.
A phenylsulfonyl group can be regarded as a hydrogen
surrogate and can easily be replaced by a hydrogen atom by
conventional means.[24] We indeed examined the selective re-
moval of one of the two phenylsulfonyl groups in a [2+2+1]
cycloaddition product (Scheme 4). The removal of the vinyl-
ic sulfone in 9b in a highly selective manner was achieved
by use of tributyltin hydride (2 equiv) in the presence of
AIBN[25] and subsequent acidic workup. Treatment of 9b
with further tributyltin hydride (excess) led to desulfonyla-
tion both at the vinylic and at the allylic positions.[26]
The unexpectedly easy formation of the bicyclo-
ACHUTNGREN[NUG 5.3.0]decadienone framework from the bisHCATUNGTRENN(UGN allene)s, particu-
larly from bis(phenylsulfonylallene) derivatives, under mild
conditions [{RhCl(CO)dppp}2] (5 mol%), CO (1 atm), tolu-
ene 808C, 1 h} encouraged us to apply this new method to
the construction of the bicycloACTHNUTRGNEUGN[6.3.0] skeleton. The prepara-
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5175

C. Mukai et al.
tive 13a in 70% yield together with its isomer 13a’ in 23%
yield (Table 2, entry 1). No interconversion between 13a
and 13a’ could be observed under the standard conditions,
so the production of these two eight-membered ring prod-
ucts could be interpreted in terms of the common intermedi-
ate 14a (Scheme 5): 14a could undergo either a 1,3-hydro-
gen shift (Ha’) to provide 13a, or a 1,5-hydrogen shift (Hb)[27]
to give 13a’ (Scheme 5). Under similar conditions, the malo-
nate derivative 12b afforded a mixture of 13b and 13b’ in
75% yield in a ratio of 1:6 (Table 2, entry 2). Interestingly,
the carbonylative [2+2+1] cycloadditions of the nitrogen
congener 12c and the oxygen congener 12d led to the for-
mation of the eight-membered ring products 13c (87%
yield) and 13d (86% yield), respectively, through exclusive
1,3-hydrogen (Ha) shifts on the side nearest to the hetero-
Scheme 4. Desulfonylation of 9b. AIBN=2,2’-azobis(isobutyronitrile).
tion of a bicycloACHTUNGTRENNUNG[6.3.0] ring system through a Pauson–
Khand-type [2+2+1] cycloaddition, in which allenynes were
used as substrates and a template effect was necessary to
attain high yields, had been reported by us previously.[13e]
Treatment of 3,8-bis(phenylsulfonyl)deca-1,2,8,9-tetraene
(12a, Table 2) under the standard ring-closing conditions
{[{RhCl(CO)dppp}2] (5 mol%), CO (1 atm), 808C in tolu-
AHCTUNGTREGaNNUN tom X in 14c or 14d (Table 2, entries 3 and 4). In the case
of the diaza derivative 12e, the desired carbonylative
[2+2+1] cycloaddition product 13e was formed in 27%
yield as a minor product after a prolonged reaction time. In-
stead, the corresponding [2+2] cycloaddition product 15e
was obtained as a major product (Table 2, entry 5). The data
in entry 6 of Table 2 indicate a significant improvement in
the yield of 13e with use of 10 mol% of the catalyst.
ene} for 3 h afforded the bicycloACTHNUGRTNEUNG[6.3.0]undecenone deriva-
Table 2. Rhodium(I)-catalyzed synthesis of bicyclo
ACHTUNGTREN[NUGN 6.3.0] compounds
through carbonylative [2+2+1] cycloadditions of bis
AHCTUNGTRENNUNG
Entry Bis
(allene)
t [h]
Products (yield)[b]
1
3
2
5
Scheme 5. Hydrogen shifts in intermediates 14.
75% (1:6)
To extend the scope of this method, we examined some
bis
A
ACHTUNGTRENNUNG
3
4
1
1
ACHTUNGTRENNUNG
(Scheme 6), prepared from l-tartrate, was subjected to the
standard reaction conditions to give the carbonylative prod-
uct 17 in 17% yield, together with the tetraene derivative 18
(34% yield); 18 may have arisen from a thermal [3,3]-sigma-
tropic rearrangement of the starting material.[28] The mono-
phenylsulfonyl substrate 19 afforded the desired product 20
in 67% yield. These results are in good agreement with pre-
dictions based on the previously discussed results shown in
Table 1
[{RhCl(CO)dppp}2] (5 mol%) in toluene under CO, the bis-
AHCTUNGTREG(NNUN phenylsulfonylallene) derivative 21 produced 22 in a quan-
titative yield as expected. It might thus be concluded that
the carbonylative [2+2+1] cycloaddition reactions of bis-
and
Scheme 2.
Upon
treatment
with
5
22
18
6[c]
[a] Reaction conditions: a solution of the bisACTHNUTRGENUG(N allene) 12 (0.1 mmol) and
AHCTUNGTRENNUNG
[{RhCl(CO)dppp}2] (5 mol%) in toluene (1 mL) was stirred at 808C
under CO. [b] Yields of isolated products. [c] Catalyst (10 mol%) was
used.
AHCTUNGTRENNUNG
5176
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 5173 – 5183

Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
FULL PAPER
Table 3. Rhodium(I)-catalyzed cycloisomerizations of undecatetraenes
23.[a]
Entry Substrate
X
Y
t [h] Product (% yield)[b]
1[c]
2
3
4
5
23a
23b
23c
23d
23e
23 f
C
CH2
NNs
NTs
NCO2Me
CH2
G
2
1
1
1
1
24a (96)
24b (71)
24c (70)
24d (67), 26d (7)
24e (67), 26e (8)
24 f (49), 26 f (26)
6
[a] Reaction conditions: a solution of 23 in toluene (0.1m or 0.05m) was
heated at reflux in the presence of [{RhCl(CO)dppp}2] under N2.
[b] Yields of isolated products. [c] Catalyst (5 mol%) was used. Ns=o-ni-
trobenzenesulfonyl.
Scheme 6. Formation of bicycloACTHNUGRTENUNG[4.3.0]nonadienones through rhodium(I)-
catalyzed carbonylative [2+2+1] cycloadditions of the bis(phenylsulfony-
lallene) derivatives 16, 19, and 21.
of the observed hydrogen shifts have not yet been deter-
mined.
isolable product (Table 3, entry 3). The two additional nitro-
gen analogues 24d and 24e were prepared in reasonable
yields (67%) accompanied by the formation of small
Rhodium(I)-catalyzed cycloisomerizations of bis(sulfonylal-
amounts of the bicyclo
(Table 3, entries 4 and 5). In the case of the fairly bulky bis-
ACHTUNGTREN(NUGN malonate) derivative 23 f a prolonged reaction time was
ACHTUNGTNER[NUNG 7.2.0] derivatives 26d and 26e
lene)s:
[7.3.0]dodecadienones through RhI-catalyzed carbonylative
[2+2+1] cycloadditions of bis(allene)s was next examined.
Dimethyl bis(3-phenylsulfonylpenta-3,4-dienyl)malonate
The
preparation
of
larger-sized
bicyclo-
T
G
necessary for consumption of the starting material to go to
completion and the desired product 24 f was obtained in
49% yield (Table 3, entry 6) along with 26 f (26% yield). It
should be emphasized that these ring-closing reactions of
acyclic substrates 23 to afford the monocyclic nine-mem-
bered ring products 24 proceeded smoothly under the stan-
dard conditions with normal concentrations (0.05 or 0.1m
solutions).[29–31] We did not need to use a high-dilution tech-
nique, although this would usually be used for forming
medium- and larger-sized rings to avoid oligomerization.
We next focused our efforts on the scope of this transfor-
mation. Treatment of the decatetraene derivatives 12 under
similar conditions effected cycloisomerizations (Table 4), re-
sulting in the easy formation of the cyclooctene derivatives
27 (27’) in high yields along with small yields of by-products
such as the carbonylative products 13 and the [2+2] cycload-
dition product 15c. The formation of compounds 13 can be
explained in terms of the participation of CO with the rho-
dium catalyst. The cycloisomerizations of compounds 12
consistently occurred in satisfactory yields under milder con-
ditions (808C) than those required for compounds 23 (reflux
temperature), which can be attributed to the entropy effect
(eight-membered versus nine-membered ring formation).
The malonate derivative 12b and the N-tosylated derivative
12c produced 27b and 27c, respectively, in a highly selective
manner and the corresponding regioisomers 27b’ and 27c’
were not formed (Table 4, entries 2 and 3). The oxygen con-
gener 12d, however, unselectively afforded the two possible
regioisomers 27d and 27d’ in a ratio of 57:43 in 92% yield
(Table 4, entry 4). In the exceptional case of 12c, the [2+2]
cycloaddition product 15c was obtained in 10% yield
(Table 4, entry 3).
(23a, Scheme 7) was exposed to [{RhCl(CO)dppp}2]
(10 mol%) under CO in toluene at reflux for 3 h by the es-
tablished procedure to produce the nine-membered monocy-
clic compound 24a in 69% yield along with a small amount
of the carbonylative product 25a (5% yield). A better yield
(33%) of 25a was recorded in xylene at reflux (1 h), but
24a was still formed in 17% yield (Scheme 7).
Scheme 7. Formation of 24a and 25a under the conditions of rhodium(I)-
catalyzed carbonylative [2+2+1] cycloaddition of 23a.
It is obvious that CO was not involved in the formation of
24a, so 23a was treated with [{RhCl(CO)dppp}2] (5 mol%)
in toluene at reflux under N2, instead of CO, to afford 24a
in 96% yield (Table 3, entry 1). The simpler undecatetraene
derivative 23b, without any substituents on its carbon
tether, also gave the corresponding compound 24b in good
yield (Table 3, entry 2). The lower yield of 24b relative to
that of 24a can be attributed to loss of the geminal disubsti-
tuted effect. The N-nosylated substrate 23c also produced
the nine-membered-ring triene 24c in 70% yield as the sole
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5177

C. Mukai et al.
Table 4. Rhodium(I)-catalyzed cycloisomerizations of decatetraenes 12.[a]
Entry Substrate Products
[h] (yield)[b]
t
1
3
2
3
4
1
Scheme 9. A plausible mechanism for the formation of compounds K
from compounds H.
2.5
4.5
J could then collapse to K in a reductive elimination pro-
cess.[33,34]
In order to clarify the plausible mechanism, the 4,4-dideu-
terated decatetraene 31 was prepared and treated in the
presence of [{RhCl(CO)dppp}2] (5 mol%) in toluene at
808C for 2 h to give 32 in 77% yield (Scheme 10). In addi-
tion, the following cross-over experiment was performed. A
mixture of 12a and 31 in toluene was treated in the presence
of [{RhCl(CO)dppp}2] to afford 27a and 32 in 82% and
93% yields, respectively, and no cross-over product was ob-
tained; accordingly, intermolecular hydrogen transfer mech-
anism was ruled out.
[a] Reaction conditions: a solution of 12 in toluene (0.1m) was heated at 808C
in the presence of [{RhCl(CO)dppp}2] (5 mol%) under N2. [b] Yields of isolat-
ed products. [c] An inseparable mixture of 27d’ and 13d in a ratio of 6:1 was
obtained.
Ma et al. reported the RhI-catalyzed cycloisomerizations
of the nonatetraene derivatives 28 (R=alkyl) resulting in
the cycloheptenes 29 with exo-methylene groups,[10] whereas
compound 28 (R=H) produced the steroidal skeleton 30
rather than 29 (Scheme 8).[9] Interestingly, the tendencies of
Scheme 10. Transformation of deuterated 31 into the cyclooctene 32.
The following experiments were performed to investigate
an alternative mechanism involving the intermediacy of cy-
clobutenes L,[21,22] as well as the possibility of a simpler ther-
mal reaction pathway (H!L!M!K) in which the RhI cat-
Scheme 8. Rhodium(I)-catalyzed cycloisomerizations of nonatetraenes
28.
alyst would not participate. A solution of the undecaACHTUNGTRENNUNGtet-
AHCTUNGTRENNUNG
raene 23a in toluene in the absence of the RhI catalyst was
compounds 23 (Table 3) and compounds 12 (Table 4), with
heated at reflux for 20 h, but no reaction occurred and 23a
was fully recovered. When heated at reflux in xylene, com-
pound 23a gradually decomposed. Although compound 23e
was converted into the [2+2] cycloadduct 26e in 52% yield
on treatment in toluene at reflux for a prolonged time
(36 h), no interconversion between the bicyclic compound
26e and the monocyclic compound 24e was observed in the
presence of RhI catalyst in toluene at reflux. Furthermore,
the decatetraene 12a was also inactive when heated in tolu-
ene at 808C for 5 h in the absence of the RhI catalyst
(Table 5, entry 1). These experiments therefore indicate not
bis(terminal allene) functionality, in RhI-catalyzed cyclo-
ACHTUNGTRENNUNGisomACHTUNGTRENNUNGerizations were obviously distinct from that of 28 (R=
H). The formation of compounds 24 and compounds 27
(compounds K, Scheme 9) from compounds 23 and com-
pounds 12 (compounds H), respectively, can be tentatively
interpreted on the basis of the assumption that the first oxi-
dative insertion of the RhI catalyst into the two terminal
double bonds of the bisACHTUNRGTNE(NUG allene) groups leads to the rhodacy-
cle intermediates I,[10,12b,32] which might be susceptible to
thermal [1,5]-H shifts (Scheme 9). The resulting compounds
5178
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 5173 – 5183

Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
FULL PAPER
Table 5. Cycloaddition and cycloisomerization of the decatetraene 12a.[a]
Table 6. Interconversion of 15a, 15a’, and 27a in xylene at reflux.[a]
Entry Solvent
T
t [h] Results (yield)[b]
1
2
3
toluene 808C
toluene reflux 72
xylene reflux 24
5
no reaction
15a (37%), 12a+15a’+27a (43%)[c,d]
15a (trace),[e] 15a’+27a (70%)[d,f]
Entry
Substrate
t [h]
Yield [%][b]
Product ratio[c]
1
2
3
4
5
6
15a
15a
15a’
15a’
27a
27a
12
17
12
17
12
17
93
45
94
68
46
33
15a/15a’/27a 2:5:5
15a’/27a 1:2
15a’/27a 9:5
15a’/27a 4:5
15a’/27a 1:2
15a’/27a 2:5
[a] Reaction conditions: a solution of 12a was heated in toluene or
xylene in the absence of [{RhCl(CO)dppp}2] under N2. [b] Yields of prod-
ucts. [c] A mixture of 12a, 15a’, and 27a in a ratio of 2:5:2 was obtained.
[d] The ratio was determined by 1H NMR. [e] Determined by TLC. [f] A
mixture of 15a’ and 27a in a ratio of 5:6 was obtained.
[a] Reaction conditions: a solution of 15a, 15a’, or 27a in xylene was
heated at reflux under N2. [b] Yield of products. [c] The ratio was deter-
1
mined by H NMR.
only that [{RhCl(CO)dppp}2] is essential for the transforma-
tions of 23 and 12 into 24 and 27, respectively, but also sup-
port the mechanism (H!I!J!K) depicted in Scheme 9 as
a major pathway.[35]
808C for 2 h to give 33a in 64% yield along with the
bicyclo
lar treatment of the nitrogen congener 8c gave 33c in only
24% yield, with the bicyclo[5.2.0] compound 10c as the
ACHTUNGTREN[NGNU 5.2.0] derivative 10a (13% yield, Scheme 11). Simi-
Cycloaddition and/or cycloisomerization of 12a did occur,
however, after prolonged reaction times at higher reaction
temperatures. The solution of 12a in toluene was heated at
reflux for 3 days to produce the [2+2] cycloaddition product
15a in 37% yield together with a mixture of 12a, [1,5]-H
shifted 15a’, and 27a (43% yield) in a ratio of 2:5:2
(Table 5, entry 2). Compounds 15a’ and 27a were major
products (70% yield, 15a’/27a 5:6) after treatment at reflux
in xylene for 1 day (Table 5, entry 3). The fact that com-
pound 15a was present only in trace amounts after treat-
ment at a higher reaction temperature (Table 5, entry 3) sug-
gests that 15a must be an initial product of 12a.
AHCTUNGTRENNUNG
major product (47% yield) of this cycloisomerization. These
relatively low yields in the RhI-catalyzed transformations of
nonatetraenes into seven-membered-ring trienes may reflect
some limitations in the flexibilities of the rhodabicyclo
intermediates I leading to J, relative to those of the
rhodabicyclo[6.3.0] and rhodabicyclo[7.3.0] derivatives
shown in Scheme 9.
ACHTUNGTRENNUNG[5.3.0]
G
ACHTUNGTRENNUNG
When 15a was heated at reflux in xylene for 12 h, 15a,
15a’, and 27a were obtained in a ratio of 2:5:5 (93% yield,
Table 6, entry 1). Use of a longer reaction time afforded
15a’ and 27a in a ratio of 1:2 in low yield, probably because
of instability of 27a at higher reaction temperatures
(Table 6, entry 2). At reflux in xylene, compounds 15a’ and
27a independently provided mixtures of 15a’ and 27a, but
never produced 15a (Table 6, entries 3–6). On the basis of
these interconversion experiments, we can interpret the
thermal transformation of 12a into 15a, 15a’, and 27a as
the following consecutive three-step process: 1) thermal
Scheme 11. Rhodium(I)-catalyzed cycloisomerizations of compounds 8.
Conclusion
In summary, we have developed novel [{RhCl(CO)dppp}2]-
[2+2] cycloaddition of bis
G
catalyzed intramolecular [2+2+1] cycloadditions of bis-
four-membered ring product 15a (L), 2) [1,5]-H shift of an
allylic proton of 15a (L), and 3) thermal 4p electrocyclic
ring-opening of the cyclobutene of 15a’ (M) to give 27a
(K)[36] [15a’ (M) and 27a (K) exist in equilibrium in xylene
at reflux] (Scheme 9). This thermal cycloaddition and/or cy-
cloisomerization of 12a described in Table 5 cannot compete
with the RhI-catalyzed cycloaddition and/or cycloisomeriza-
tion of 12, because the latter reaction proceeded easily at
lower reaction temperatures.[37]
N
ACHTUNGTRENNUNG
E
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
Finally we examined the formation of seven-membered-
ring triene derivatives. The nonatetraene 8a was treated in
the presence of [{RhCl(CO)dppp}2] (5 mol%) in toluene at
struction of 2,6-bis(phenylsulfonyl)bicyclo
one and 2,5-bis(phenylsulfonyl)bicyclo[4.3.0]
skeletons in high yields. We also developed novel
G
ACHTUNGTRENNUNG
R
G
N
ACHTUNGTRENNUNG
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5179

C. Mukai et al.
found: 572.1170; elemental analysis calcd (%) for C28H28O9S2: C 58.73, H
4.93; found: C 58.36, H 4.87.
[{RhCl(CO)dppp}2]-catalyzed easy transformations of 3,9-
bis(phenylsulfonyl)undeca-1,2,9,10-tetraene derivatives into
the corresponding 3,4-dimethylene-2,5-bis(phenylsulfonyl)-
cyclononene framework. The newly developed procedure
proceeded under conditions with normal concentrations
(0.05 or 0.1m solution) and is applicable to the construction
of one- and two-carbon shortened eight- and seven-mem-
bered monocyclic skeletons in reasonable yields. The plausi-
ACHTUNGTRENNUNG
General procedure for cycloisomerization: [{RhCl(CO)dppp}2] (5 or
10 mol%) was added to a solution of the bisACTHNUTRGNEU(GN allene) (0.1 mmol) in tolu-
G
E
G
A
A
ACHTUNGTRENNUNG
ene (1 mL). The reaction mixture was heated under N2 at 808C or at
reflux temperature until the complete disappearance of the starting mate-
rial (monitored by TLC). Toluene was evaporated off, and the residual
oil was chromatographed with hexane/AcOEt or CH2Cl2/AcOEt to
afford the cyclized product. Chemical yields are summarized in Tables 3
and 4 and in Schemes 10 and 11.
ble mechanism behind this transformation of bisACTHNUTRGNEUG(N allene)s
(E)-3,4-Dimethylene-2,5-bis(phenylsulfonyl)cyclononene (24b): Com-
pound 24b was obtained as colorless crystals; m.p. 192–1938C (AcOEt);
1H NMR (500 MHz): d=7.85–7.40 (m, 10H), 7.09 (dd, J=12.5, 5.9 Hz,
1H), 5.69 (s, 1H), 5.47 (s, 1H), 4.91 (s, 1H), 4.63 (s, 1H), 3.26–3.23 (m,
1H), 2.76 (qd, J=12.9, 5.2 Hz, 1H), 2.64 (dd, J=14.2, 9.5 Hz, 1H), 2.17–
2.11 (m, 1H), 1.98–1.92 (m, 1H), 1.84–1.76 (m, 1H), 1.65–1.55 (m, 2H),
1.33–1.25 ppm (m, 1H); 13C NMR (126 MHz): d=145.9, 144.8, 140.0,
138.9, 138.8, 137.5, 133.6, 133.2, 129.6, 129.3, 128.7, 128.6, 121.3, 120.5,
68.7, 30.3, 27.4, 26.63, 26.57 ppm; LRMS (EI): m/z (%): 428 (0.3) [M]+;
elemental analysis calcd (%) for C23H24O4S2: C 64.46, H 5.64; found: C
64.37, H 5.69.
into the medium-sized monocyclic derivatives was investi-
gated through several additional experiments. The addition-
al scope and limitations of these methods, as well as their
application to the synthesis of natural products, are current-
ly under investigation.
Experimental Section
(E)-5,6-Dimethylene-1-(2-nitrophenylsulfonyl)-4,7-bis(phenylsulfonyl)-
2,3,4,5,6,9-hexahydro-1H-azonine (24c): Compound 24c was
a white
powder; m.p. 94.5–96.58C (hexane/AcOEt); 1H NMR (500 MHz): d=
8.00–7.99 (m, 1H), 7.84–7.82 (m, 2H), 7.76–7.58 (m, 9H), 7.51 (t, J=
7.8 Hz, 2H), 7.00 (dd, J=10.5, 6.3 Hz, 1H), 5.64 (d, J=1.2 Hz, 1H), 5.59
(s, 1H), 5.19 (s, 1H), 4.97 (s, 1H), 4.13 (dd, J=14.6, 6.3 Hz, 1H), 3.96
(dd, J=14.6, 10.5 Hz, 1H), 3.62–3.56 (m, 2H), 3.31–3.26 (m, 1H), 2.53–
2.47 (m, 1H), 2.04–1.96 ppm (m, 1H); 13C NMR (67.8 MHz): d=148.0,
144.8, 142.2, 138.6, 137.6, 137.1, 135.4, 134.2, 134.1, 133.7, 131.9, 131.8,
131.2, 129.6, 129.4, 129.2, 128.9, 124.4, 122.8, 121.6, 65.6, 47.2, 45.7,
31.3 ppm; LRMS (FAB+): m/z (%): 615 (7.9) [M+H]+; HRMS
General methods: Melting points are uncorrected. IR spectra were mea-
sured in CHCl3. 1H NMR spectra were measured in CDCl3. CHCl3
(7.26 ppm) for silyl compounds and tetramethylsilane (0.00 ppm) for
compounds without a silyl group were used as internal standards unless
otherwise stated. 13C NMR spectra were recorded in CDCl3 with CDCl3
(77.00 ppm) as an internal standard unless otherwise stated. All reactions
were carried out under nitrogen unless otherwise stated. Silica gel (silica
gel 60, 230–400 mesh) was used for chromatography. Organic extracts
were dried over anhydrous Na2SO4.
AHCTUNGTRENNUNG
General procedure for carbonylative [2+2+1] cycloadditions under CO:
The rhodium(I) catalyst (5~10 mol%) was added to a solution of the bis-
A
a
powder; m.p. 97.5–98.58C (hexane/Et2O); 1H NMR (500 MHz): d=7.84–
7.83 (m, 2H), 7.72–7.50 (m, 10H), 7.31 (d, J=8.1 Hz, 2H), 6.98 (dd, J=
9.0, 6.1 Hz, 1H), 5.53 (d, J=1.2 Hz, 1H), 5.41 (s, 1H), 5.25 (s, 1H), 5.06
(s, 1H), 3.99 (dd, J=15.1, 6.1 Hz, 1H), 3.70 (dd, J=11.5, 2.7 Hz, 1H),
3.58 (dd, J=15.1, 9.0 Hz, 1H), 3.32–3.23 (m, 2H), 2.44 (s, 3H), 2.40–2.34
(m, 1H), 1.99–1.92 ppm (m, 1H); 13C NMR (126 MHz): d=144.3, 144.1,
141.6, 138.8, 137.9, 137.4, 136.0, 135.0, 133.9, 133.7, 130.0, 129.5, 129.3,
129.2, 128.9, 127.2, 122.4, 121.2, 65.7, 48.1, 47.0, 30.7, 21.5 ppm; LRMS
(FAB+): m/z (%): 584 (30.0) [M+H]+; HRMS (FAB+): m/z: calcd for
C29H30NO6S3: 584.1235; found: 584.1243.
at 808C under CO until the complete disappearance of the starting mate-
rial (monitored by TLC). Toluene was evaporated off, and the residual
oil was chromatographed with hexane/AcOEt or CH2Cl2/AcOEt to
afford the cyclized product. Chemical yields are summarized in Tables 1
and 2 and in Scheme 2 and Scheme 6. Characterization data for the prod-
ucts are given in the Supporting Information of ref. [14].
(E)-8,8-Bis(methoxycarbonyl)-3,4-dimethylene-2,5-bis(phenylsulfonyl)cy-
clononene (24a) and 5,5-bis(methoxycarbonyl)-2,8-bis
G
(4.9 mg, 4.2ꢁ10ꢀ3 mmol) was added to a solution of 23a (23.0 mg, 4.22ꢁ
10ꢀ2 mmol) in xylene (1.0 mL). The reaction mixture was heated at reflux
for 1 h under CO. Xylene was evaporated off, and the residual oil was
chromatographed with CH2Cl2/AcOEt (20:1 to 8:1) to afford 24a
(4.0 mg, 17%) and 25a (7.9 mg, 33%).
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
crystals; m.p. 255–2568C (AcOEt); 1H NMR (500 MHz): d=7.95–7.94
(m, 4H), 7.68–7.65 (m, 2H), 7.60–7.57 (m, 4H), 7.41 (d, J=8.2 Hz, 2H),
7.24 (d, J=8.2 Hz, 2H), 3.20 (t, J=6.0 Hz, 4H), 3.16 (s, 4H), 2.91 (t, J=
6.0 Hz, 4H), 2.40 ppm (s, 3H); 13C NMR (67.8 MHz): d=154.2, 143.4,
140.2, 136.5, 133.6, 132.1, 129.7, 129.3, 128.1, 126.8, 49.8, 31.0, 29.5,
21.5 ppm; LRMS (FAB+): m/z (%): 584 (3.0) [M+H]+; HRMS
Compound 24a: White powder; m.p. 136–137.58C (hexane/AcOEt);
1H NMR (500 MHz): d=7.79–7.41 (m, 10H), 6.93 (dd, J=13.9, 4.0 Hz,
1H), 5.71 (s, 1H), 5.60 (s, 1H), 5.06 (s, 1H), 4.83 (s, 1H), 3.76 (s, 3H),
3.73 (s, 3H), 3.41 (t, J=13.9 Hz, 1H), 3.11 (d, J=9.8 Hz, 1H), 2.69–2.56
(m, 3H), 1.71–1.52 ppm (m, 2H); 13C NMR (126 MHz): d=170.7, 170.1,
145.4, 141.1, 139.3, 139.1, 138.4, 137.1, 133.8, 133.4, 129.6, 129.4, 128.8,
128.6, 122.1, 121.3, 68.0, 57.0, 53.2, 53.1, 32.6, 31.9, 26.4 ppm; IR: n˜ =
1732 cmꢀ1; LRMS (EI): m/z (%): 544 (39.2) [M]+; HRMS (EI): m/z:
calcd for C27H28O8S2: 544.1226, found: 544.1227; elemental analysis calcd
(%) for C27H28O8S2: C 59.54, H 5.18; found: C 59.38, H 5.18.
AHCTUNGTRENNUNG
a
white
powder; m.p. 87–898C (hexane/AcOEt); 1H NMR (270 MHz,
[D6]DMSO, 1208C): d=7.80–7.71 (m, 6H), 7.66–7.59 (m, 4H), 6.95 (t,
J=5.9 Hz, 1H), 5.40 (s, 1H), 5.28 (s, 1H), 5.20 (s, 1H), 4.94 (s, 1H),
3.92–3.77 (m, 3H), 3.52 (s, 3H), 3.39 (ddd, J=14.8, 6.4, 4.6 Hz, 1H), 3.25
(ddd, J=14.8, 7.3, 4.6 Hz, 1H), 2.28–2.09 ppm (m, 2H); 13C NMR
(126 Hz, [D6]DMSO, 1208C): d=155.0, 142.9, 139.9, 138.1, 137.7, 137.5,
137.4, 133.3, 133.2, 128.8, 128.5, 128.2, 127.9, 120.8, 119.7, 66.9, 51.8, 47.1,
27.4, 13.4 ppm; IR: n˜ =1701 cmꢀ1; LRMS (FAB+): m/z (%): 488 (56.1)
[M+H]+; HRMS (FAB+): m/z: calcd for C24H26NO6S2: 488.1202; found:
488.1209.
Compound 25a: White powder; m.p. 210–2128C (hexane/AcOEt);
1H NMR (500 MHz): d=7.83–7.78 (m, 4H), 7.70–7.67 (m, 2H), 7.60–7.57
(m, 4H), 7.24 (s, 1H), 4.49 (dd, J=9.5, 2.9 Hz, 1H), 3.72–3.67 (m, 4H),
3.49 (s, 3H), 3.10 (d, J=21.5 Hz, 1H), 3.02–2.98 (m, 2H), 2.51–2.39 (m,
3H), 2.14–2.09 (m, 1H), 2.02–1.96 (m, 1H), 1.66–1.58 ppm (m, 1H);
13C NMR (67.8 MHz): d=200.5, 171.6, 170.9, 162.5, 145.4, 139.8, 139.7,
139.6, 137.3, 134.4, 134.1, 129.61, 129.59, 128.8, 127.7, 65.0, 56.9, 53.2,
52.5, 41.5, 34.8, 29.7, 27.0, 24.1 ppm; IR: n˜ =1728 cmꢀ1; LRMS (EI): m/z
(%): 572 (34.5) [M]+; HRMS (EI): m/z: calcd for C28H28O9S2: 572.1175,
G
ACHTUNGTRENNUNG[7.2.0]-
AHCTUNGTRENNUNG
5180
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 5173 – 5183

Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
FULL PAPER
1
878C (hexane/AcOEt); H NMR (270 MHz): d=7.96 (d, J=6.7 Hz, 2H),
m/z (%): 570 (27.6) [M+H]+; elemental analysis calcd (%) for
7.87 (d, J=7.0 Hz, 2H), 7.69–7.55 (m, 6H), 3.69 (s, 3H), 3.69–3.62 (m,
2H), 3.35–3.32 (m, 2H), 3.23–3.16 (m, 4H), 2.83–2.81 ppm (m, 4H);
13C NMR (100 MHz, [D6]DMSO, 1508C): d=155.4, 150.9, 140.3, 133.1,
132.8, 128.6, 126.6, 51.5, 46.1, 29.8, 29.0 ppm; IR: n˜ =1695 cmꢀ1; LRMS
(FAB+): m/z (%): 488 (32.0) [M+H]+; HRMS (FAB+): m/z: calcd for
C24H26NO6S2: 488.1202; found: 488.1208.
C28H27NO6S3: C 59.03, H 4.78, N 2.46; found: C 58.95, H 4.73, N 2.25.
(E)-5,6-Dimethylene-4,7-bis(phenylsulfonyl)-3,4,5,6-tetrahydro-2H-oxo-
cine (27d): Compound 27d was a white solid; 1H NMR (500 MHz): d=
7.76 (d, J=7.8 Hz, 2H), 7.70 (s, 1H), 7.66–7.60 (m, 4H), 7.53–7.48 (m,
4H), 5.48 (s, 1H), 5.47 (s, 1H), 5.39 (s, 1H), 5.32 (s, 1H), 4.83–4.78 (m,
1H), 4.13–4.09 (m, 1H), 3.75 (dd, J=10.5, 4.2 Hz, 1H), 2.42–2.28 ppm
(m, 2H); 13C NMR (126 MHz): d=155.6, 140.1, 139.3, 137.9, 136.5, 133.7,
133.1, 129.14, 129.11, 128.6, 128.0, 122.7, 119.9, 118.3, 66.4, 63.6,
31.2 ppm; LRMS (EI): m/z (%): 416 (0.9) [M]+; HRMS (EI): m/z: calcd
for C21H20O5S2: 416.0752; found: 416.0753.
(E)-7,7,9,9-Tetrakis(methoxycarbonyl)-3,4-dimethylene-2,5-bis(phenylsul-
fonyl)cyclononene (24 f): Compound 24 f was obtained as colorless nee-
dles; m.p. 221–222.58C (AcOEt); 1H NMR (270 MHz): d=8.10–8.07 (m,
2H), 7.87–7.84 (m, 2H), 7.69–7.51 (m, 7H), 5.97 (s, 1H), 5.85 (s, 1H),
5.44 (s, 1H), 4.55 (d, J=12.2 Hz, 1H), 3.99 (brs, 1H), 3.79 (s, 3H), 3.70
(s, 3H), 3.52 (s, 3H), 3.47 (s, 3H), 3.460 (s, 1H), 3.456 (s, 1H), 2.74 (dd,
J=13.5, 1.6 Hz, 1H), 2.15 ppm (dd, J=13.5, 12.2 Hz, 1H); 13C NMR
(126 MHz): d=171.5, 169.8, 169.3, 167.3, 142.9, 139.9, 139.4, 137.9, 137.8,
136.8, 134.0, 133.5, 129.8, 129.7, 129.0, 128.7, 121.4, 120.2, 61.8, 56.2, 54.4,
54.0, 53.6, 53.4, 53.0, 38.8, 34.8 ppm; IR: n˜ =1744 cmꢀ1; LRMS (EI): m/z
(%): 660 (0.1) [M]+; HRMS (EI): m/z: calcd for C31H32O12S2: 660.1336;
found: 660.1336.
(E)-4,5-Dimethylene-3,6-bis(phenylsulfonyl)-3,4,5,8-tetrahydro-2H-oxo-
cine (27d’): Compound 27d’ was a white solid; 1H NMR (500 MHz): d=
7.80–7.79 (m, 2H), 7.68–7.53 (m, 6H), 7.46–7.43 (m, 2H), 7.15 (t, J=
5.0 Hz, 1H), 5.37 (s, 1H), 5.33 (s, 1H), 5.10 (s, 1H), 5.09 (s, 1H), 4.51
(dd, J=16.6, 5.1 Hz, 1H), 4.27 (dd, J=11.7, 6.8 Hz, 1H), 4.23 (dd, J=
16.6, 5.1 Hz, 1H), 4.05 (dd, J=11.7, 3.2 Hz, 1H), 3.69 ppm (dd, J=6.8,
3.2 Hz, 1H); 13C NMR (126 MHz): d=141.4, 140.0, 138.4, 138.2, 138.1,
137.8, 133.7, 133.6, 129.1, 129.0, 128.9, 128.8, 122.3, 122.1, 69.6, 68.1,
67.3 ppm; LRMS (EI): m/z (%): 416 (0.5) [M]+; HRMS (EI): m/z: calcd
for C21H20O5S2: 416.0752; found: 416.0750.
ACHTUNGTRENNUNG
A
R
a white
powder; m.p. 75–768C (iPr2O/hexane); 1H NMR (500 MHz): d=7.83–
7.81 (m, 4H), 7.65–7.62 (m, 2H), 7.56–7.53 (m, 4H), 3.77 (s, 6H), 3.68 (s,
6H), 3.51 (d, J=17.1 Hz, 2H), 3.10 (d, J=17.1 Hz, 2H), 3.023 (s, 1H),
3.020 (s, 1H), 2.96–2.93 (m, 2H), 2.76–2.73 ppm (m, 2H); 13C NMR
(67.8 MHz): d=170.7, 169.8, 154.4, 140.6, 134.8, 133.7, 129.3, 127.8, 57.2,
53.4, 53.0, 31.7, 31.2, 30.5 ppm; IR: n˜ =1740 cmꢀ1; LRMS (EI): m/z (%):
660 (0.2) [M]+; HRMS (EI): m/z: calcd for C31H32O12S2: 660.1336; found:
660.1337.
3,4-Dimethylene-2,5-bis(phenylsulfonyl)cycloheptene (33a): Compound
33a was obtained as colorless needles; m.p. 170–1728C (AcOEt);
1H NMR (500 MHz): d=7.78–7.74 (m, 4H), 7.64–7.61 (m, 1H), 7.58–7.56
(m, 1H), 7.53–7.46 (m, 4H), 7.17–7.15 (m, 1H), 5.93 (s, 1H), 5.05 (s, 1H),
4.72 (s, 1H), 4.23 (s, 1H), 3.77 (dd, J=11.7, 4.2 Hz, 1H), 2.87–2.81 (m,
1H), 2.42–2.23 ppm (m, 3H); 13C NMR (126 MHz): d=142.1, 140.0,
139.9, 139.2, 137.0, 136.3, 133.9, 133.1, 129.4, 129.0, 128.7, 128.5, 123.8,
122.0, 69.6, 28.1, 23.2 ppm; LRMS (EI): m/z (%): 400 (0.2) [M]+; HRMS
(EI): m/z: calcd for C21H20O4S2: 400.0803; found: 400.0799.
(E)-3,4-Dimethylene-2,5-bis(phenylsulfonyl)cyclooctene (27a): Com-
pound 27a was
a
white solid; m.p. 133–1348C (AcOEt); 1H NMR
2,6-Bis(phenylsulfonyl)bicycloACTHNUTRGNE[NUG 5.2.0]nona-1,6-diene (10a): Compound
(500 MHz): d=7.78 (d, J=7.6 Hz, 2H), 7.73 (t, J=7.3 Hz, 1H), 7.65–7.62
(m, 2H), 7.50 (t, J=7.3 Hz, 1H), 7.35–7.23 (m, 5H), 5.63 (s, 2H), 5.46 (s,
1H), 4.80 (s, 1H), 3.23 (d, J=12.0 Hz, 1H), 2.61–2.54 (m, 2H), 2.42–2.37
(m, 1H), 2.20–2.17 (m, 1H), 2.00–1.92 (m, 1H), 1.56–1.52 ppm (m, 1H);
13C NMR (67.8 MHz): d=145.7, 144.5, 139.4, 138.3, 137.6, 137.1, 133.3,
133.1, 129.3, 129.0, 128.6, 128.1, 120.8, 120.7, 66.0, 29.5, 25.4, 24.0 ppm;
LRMS (EI): m/z (%): 414 (5.9) [M]+; elemental analysis calcd (%) for
C22H22O4S2: C 63.74, H 5.35; found: C 63.42, H 5.38.
10a was obtained as colorless needles; m.p. 185–1878C (hexane/AcOEt);
1H NMR (500 MHz): d=7.86–7.84 (m, 4H), 7.65–7.63 (m, 2H), 7.57–7.54
(m, 4H), 3.25 (s, 4H), 2.48 (t, J=5.4 Hz, 4H), 1.80–1.76 ppm (m, 2H);
13C NMR (67.8 MHz): d=148.9, 140.0, 138.4, 133.7, 129.3, 127.6, 30.5,
30.4, 22.7 ppm; LRMS (EI): m/z (%): 400 (4.6) [M]+; elemental analysis
calcd (%) for C21H20O4S2: C 62.98, H 5.03; found: C 63.12, H 5.10.
4,5-Dimethylene-1-(4-methylphenylsulfonyl)-3,6-bis(phenylsulfonyl)-
2,3,4,5-tetrahydro-1H-azepine (33c): Compound 33c was
a white
(E)-3,3-Bis(methoxycarbonyl)-7,8-dimethylene-1,6-bis(phenylsulfonyl)cy-
powder; 158–1628C (hexane/AcOEt); 1H NMR (500 MHz): d=8.11 (s,
1H), 7.77–7.74 (m, 4H), 7.71–7.66 (m, 3H), 7.56–7.53 (m, 3H), 7.47–7.44
(m, 2H), 7.39 (d, J=8.1 Hz, 2H), 5.91 (s, 1H), 5.00 (s, 1H), 4.54 (s, 1H),
4.21 (s, 1H), 4.21–4.17 (m, 2H), 3.78 (dd, J=14.6, 13.0 Hz, 1H), 2.49 ppm
(s, 3H); 13C NMR (67.8 MHz): d=145.9, 140.1, 139.3, 137.2, 136.2, 134.7,
134.4, 133.7, 133.0, 130.6, 129.4, 129.2, 128.7, 128.1, 127.4, 123.4, 123.1,
119.5, 69.2, 45.1, 21.7 ppm; LRMS (EI): m/z (%): 555 (0.1) [M]+; HRMS
(EI): m/z: calcd for C27H25NO6S3: 555.0844; found: 555.0848.
clooctene (27b): Compound 27b was
a
colorless solid; 1H NMR
(400 MHz): d=7.81–7.79 (m, 2H), 7.67–7.62 (m, 4H), 7.60–7.52 (m, 4H),
7.45 (s, 1H), 5.71 (s, 1H), 5.55 (s, 1H), 5.51 (s, 1H), 5.19 (s, 1H), 3.72 (s,
3H), 3.59 (dd, J=12.2, 3.7 Hz, 1H), 3.45 (s, 3H), 2.84–2.77 (m, 1H),
2.21–2.05 (m, 2H), 1.73–1.64 ppm (m, 1H); 13C NMR (126 MHz): d=
169.2, 167.6, 142.0, 138.12, 138.10, 138.0, 137.4, 136.3, 133.9, 133.5, 129.4,
129.0, 128.7, 128.6, 122.3, 117.9, 62.9, 60.0, 53.5, 53.2, 26.9, 26.5 ppm; IR:
n˜ =1736 cmꢀ1; LRMS (EI): m/z (%): 530 (0.7) [M]+; HRMS (EI): m/z:
calcd for C26H26O8S2: 530.1069; found: 530.1067.
Crossover experiment: [{RhCl(CO)dppp}2] (3.3 mg, 3.3ꢁ10ꢀ3 mmol) was
added at room temperature to a solution of bis
ACHTUNGTREN(NUNG allene) 12a (13.6 mg,
(E)-5,6-Dimethylene-1-(4-methylphenylsulfonyl)-4,7-bis(phenylsulfonyl)-
1,2,3,4,5,6-hexahydroazocine (27c): Compound 27c was a white powder;
m.p. 184–1858C (acetone); 1H NMR (270 MHz): d=8.29 (s, 1H), 7.78–
7.46 (m, 12H), 7.36 (d, J=8.4 Hz, 2H), 5.58 (s, 1H), 5.40 (s, 1H), 5.31 (s,
1H), 5.12 (s, 1H), 4.05–3.94 (m, 1H), 3.74–3.62 (m, 2H), 2.46 (s, 3H),
2.16–2.09 ppm (m, 2H); 13C NMR (67.8 MHz): d=145.5, 139.6, 138.3,
137.9, 136.9, 136.6, 134.5, 133.9, 133.2, 130.4, 129.2, 129.1, 128.3, 128.1,
127.3, 124.0, 118.2, 117.9, 63.6, 42.4, 30.9, 21.7 ppm; LRMS (FAB+): m/z
(%): 570 (34.7) [M+H]+; HRMS (FAB+): m/z: calcd for C28H28NO6S3:
570.1079; found: 570.1077.
3.28ꢁ10ꢀ2 mmol) and bis(allene) 31 (17.4 mg, 3.28ꢁ10ꢀ2 mmol) in tolu-
AHCTUNGTRENNUNG
ene (1.2 mL). After stirring for 2.5 h at 808C, the reaction mixture was
concentrated to dryness. The residue was chromatographed with CHCl3/
AcOEt (40:1) to afford 27a (11.1 mg, 82%) as a white solid and 32
(16.1 mg, 93%) as a white solid.
(E)-[2,6-2H2]-3,3-Bis(methoxycarbonyl)-7,8-dimethylene-1,6-bis(phenyl-
fonyl)cyclooctene (32): Compound 32 was a white solid; 1H NMR
ACHUTNGRENsNUG ulACHTUNGTRENNUGN
(400 MHz): d=7.81–7.80 (m, 2H), 7.70–7.62 (m, 4H), 7.60–7.52 (m, 4H),
5.70 (s, 1H), 5.55 (s, 1H), 5.52 (s, 1H), 5.19 (s, 1H), 3.72 (s, 3H), 3.45 (s,
3H), 2.84–2.76 (m, 1H), 2.21–2.15 (m, 1H), 2.10–2.05 (m, 1H), 1.72–
1.65 ppm (m, 1H); IR: n˜ =1736 cmꢀ1; LRMS (EI): m/z (%): 532 (1.6)
[M]+; HRMS (EI): m/z: calcd for C26H24D2O8S2: 532.1195; found:
532.1193.
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
plates; m.p. 229–2308C (AcOEt); 1H NMR (500 MHz): d=7.96 (d, J=
7.3 Hz, 2H), 7.89 (d, J=7.3 Hz, 2H), 7.78–7.75 (m, 1H), 7.69–7.64 (m,
3H), 7.59–7.56 (m, 2H), 7.19–7.14 (m, 4H), 4.14 (s, 2H), 3.43 (t, J=
5.9 Hz, 2H), 3.00 (t, J=8.3 Hz, 2H), 2.77 (t, J=8.3 Hz, 2H), 2.61 (t, J=
5.9 Hz, 2H), 2.40 ppm (s, 3H); 13C NMR (126 MHz): d=151.8, 151.5,
143.5, 139.9, 139.2, 136.6, 134.2, 133.9, 132.2, 131.8, 129.7, 129.5, 129.4,
128.1, 128.0, 126.8, 49.3, 46.0, 31.1, 30.8, 27.9, 21.5 ppm; LRMS (FAB+):
General procedure for thermal reaction: A solution of bisACTHNUTRGNE(NUG allene) in tolu-
ene or xylene was heated at reflux under N2 for the given period of time
(see Tables 5 and 6). The solvent was evaporated off, and the residual oil
was chromatographed with hexane/AcOEt or CH2Cl2/AcOEt to afford
the cyclized product. Chemical yields are summarized in Tables 5 and 6.
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5181

C. Mukai et al.
A
E
agaki, T. Yoshida, K. Yoshitani, Y. Hara, S. Kitagaki, J. Org. Chem.
2005, 70, 7159–7171; e) C. Mukai, T. Hirose, S. Teramoto, S. Kitaga-
ki, Tetrahedron 2005, 61, 10983–10994; f) F. Inagaki, T. Kawamura,
C. Mukai, Tetrahedron 2007, 63, 5154–5160.
pound 15a was obtained as colorless needles; m.p. 164.5–165.58C
(AcOEt); 1H NMR (500 MHz): d=7.86 (d, J=7.3 Hz, 4H), 7.64 (d, J=
7.3 Hz, 2H), 7.57–7.54 (m, 4H), 3.18 (s, 4H), 2.44 (brs, 4H), 1.65–
1.64 ppm (m, 4H); 13C NMR (67.8 MHz): d=150.4, 140.0, 135.4, 133.7,
129.3, 127.7, 31.3, 26.9, 24.4 ppm; LRMS (EI): m/z (%): 414 (3.8) [M]+;
elemental analysis calcd (%) for C22H22O4S2: C 63.74, H 5.35; found: C
63.37, H 5.37.
[14] Part of this work was published as a preliminary communication: F.
Inagaki, S. Narita, T. Hasegawa, S. Kitagaki, C. Mukai, Angew.
Chem. 2009, 121, 2041–2045; Angew. Chem. Int. Ed. 2009, 48, 2007–
2011.
[15] For construction of seven- and larger-membered rings through the
Pauson–Khand reaction of enynes with aromatic rings as a template,
see: a) L. Pꢂrez-Serrano, L. Casarrubios, G. Domꢃnguez, J. Pꢂrez-
Castells, Chem. Commun. 2001, 2602–2603; b) M. E. Krafft, Z. Fu,
L. V. R. BoÇaga, Tetrahedron Lett. 2001, 42, 1427–1431; c) C. J.
Lovely, H. Seshadri, B. R. Wayland, A. W. Cordes, Org. Lett. 2001,
3, 2607–2610.
(E)-2,7-Bis(phenylsulfonyl)bicycloACTHNUTRGENUGN[6.2.0]deca-1(8),2-diene (15a’): Com-
pound 15a’ was obtained as colorless needles; m.p. 151.5–152.58C
(hexane/AcOEt); 1H NMR (500 MHz): d=7.77 (d, J=7.3 Hz, 2H), 7.73
(d, J=7.3 Hz, 2H), 7.63 (t, J=7.6 Hz, 1H), 7.59 (t, J=7.4 Hz, 1H), 7.51–
7.46 (m, 4H), 7.00 (t, J=8.3 Hz, 1H), 3.88 (d, J=8.8 Hz, 1H), 2.72–2.69
(m, 1H), 2.54–2.33 (m, 5H), 2.07–2.03 (m, 1H), 1.94–1.86 (m, 1H), 1.78–
1.61 ppm (m, 2H); 13C NMR (126 Hz): d=141.5, 141.4, 141.1, 140.5,
137.7, 136.4, 133.8, 133.3, 129.14, 129.13, 128.5, 127.5, 67.7, 31.3, 30.1,
26.7, 24.9, 23.0 ppm; LRMS (EI): m/z (%): 414 (6.3) [M]+; elemental
analysis calcd (%) for C22H22O4S2: C 63.74, H 5.35; found: C 63.67, H
5.38.
[16] RhI-catalyzed carbonylative [2+2+1] cycloaddition was first report-
ed by Narasaka and Jeong. See: a) Y. Koga, T. Kobayashi, K. Nara-
saka, Chem. Lett. 1998, 249–250; b) T. Kobayashi, Y. Koga, K. Nara-
saka, J. Organomet. Chem. 2001, 624, 73–87; c) N. Jeong, S. Lee,
B. K. Sung, Organometallics 1998, 17, 3642–3644; d) N. Jeong, B. K.
Sung, Y. K. Choi, J. Am. Chem. Soc. 2000, 122, 6771–6772.
[17] Brummond independently developed the [{RhCl(CO)2}2]-catalyzed
[2+2+1] cycloaddition of allenynes. See: a) K. M. Brummond, H.
Chen, K. D. Fisher, A. D. Kerekes, B. Rickards, P. C. Sill, S. J. Geib,
Org. Lett. 2002, 4, 1931–1934; b) K. M. Brummond, D. Gao, Org.
Lett. 2003, 5, 3491–3494; c) K. M. Brummond, B. Mitasev, Org. Lett.
2004, 6, 2245–2248; d) K. M. Brummond, D. P. Curran, B. Mitasev,
S. Fischer, J. Org. Chem. 2005, 70, 1745–1753; e) K. M. Brummond,
D. Chen, Org. Lett. 2008, 10, 705–708; f) K. M. Brummond, D.
Chen, M. M. Davis, J. Org. Chem. 2008, 73, 5064–5068.
[18] Intramolecular allenic [2+2+1] cycloaddition was first reported by
Narasaka and Brummond. See: a) K. Narasaka, T. Shibata, Chem.
Lett. 1994, 315–318; b) T. Shibata, Y. Koga, K. Narasaka, Bull.
Chem. Soc. Jpn. 1995, 68, 911–919; c) J. L. Kent, H. Wan, K. M.
Brummond, Tetrahedron Lett. 1995, 36, 2407–2410; d) K. M. Brum-
mond, H. Wan, J. L. Kent, J. Org. Chem. 1998, 63, 6535–6545.
[19] For reviews of allenic [2+2+1] cycloaddition, see: a) K. M. Brum-
mond in Advances in Cycloaddition, Vol. 6 (Ed.: M. Harmata),
Elsevier, Oxford, 1999, pp. 211–237; b) B. Alcaide, P. Almendros,
Eur. J. Org. Chem. 2004, 3377–3383.
Acknowledgements
This work was supported in part by a Grant-in Aid for Scientific Re-
search from the Ministry of Education, Culture, Sports, Science, and
Technology, Japan, for which we are thankful.
[1] a) I. U. Khand, G. R. Knox, P. L. Pauson, W. E. Watts, J. Chem. Soc.
Chem. Commun. 1971, 36; b) I. U. Khand, G. R. Knox, P. L. Pauson,
W. E. Watts, M. I. Foreman, J. Chem. Soc. Perkin Trans. 1 1973,
977–981.
[2] For selected reviews, see: a) O. Geis, H.-G. Schmalz, Angew. Chem.
1998, 110, 955–958; Angew. Chem. Int. Ed. 1998, 37, 911–914;
b) K. M. Brummond, J. L. Kent, Tetrahedron 2000, 56, 3263–3283;
c) S. E. Gibson (nꢂe Thomas), A. Stevenazzi, Angew. Chem. 2003,
115, 1844–1854; Angew. Chem. Int. Ed. 2003, 42, 1800–1810; d) J.
Blanco-Urgoiti, L. AÇorbe, L. Pꢂrez-Serrano, G. Domꢃnguez, J.
Pꢂrez-Castells, Chem. Soc. Rev. 2004, 33, 32–42; e) L. V. R. BoÇaga,
M. E. Krafft, Tetrahedron 2004, 60, 9795–9833; f) T. Shibata, Adv.
Synth. Catal. 2006, 348, 2328–2336.
[3] E. Negishi, D. Choueiry, T. B. Nguyen, D. R. Swanson, N. Suzuki, T.
Takahashi, J. Am. Chem. Soc. 1994, 116, 9751–9752.
[4] P. A. Wender, M. P. Croatt, N. M. Deschamps, J. Am. Chem. Soc.
2004, 126, 5948–5949.
[5] Wender reported that several bis-enes failed to give the [2+2+1]
products under the optimized [{RhCl(CO)2}2]-catalyzed conditions
(reference [4]).
[6] T. Makino, K. Itoh, J. Org. Chem. 2004, 69, 395–405.
[7] F. Inagaki, C. Mukai, Org. Lett. 2006, 8, 1217–1220.
[8] X. Jiang, X. Cheng, S. Ma, Angew. Chem. 2006, 118, 8177–8181;
Angew. Chem. Int. Ed. 2006, 45, 8009–8013.
[20] For examples of the thermal [2+2] cycloaddition of bisACTHNUTRGNE(UNG allene)s, see:
a) S. Kitagaki, Y. Okumura, C. Mukai, Tetrahedron 2006, 62, 10311–
10320; b) reference [8] and references therein.
[21] For the metal-catalyzed [2+2] cycloaddition, see: M. Lautens, W.
Klute, W. Tam, Chem. Rev. 1996, 96, 49–92.
[22] For the metal-catalyzed [2+2] cycloaddition of allene, see: allen-
AHCTUNGTREGyNNNU nes: a) Q. Shen, G. B. Hammond, J. Am. Chem. Soc. 2002, 124,
6534–6535; b) C. H. Oh, A. K. Gupta, D. I. Park, N. Kim, Chem.
Commun. 2005, 5670–5672. RhI-catalyzed reaction was described in
this paper. Bis
tween two allenic internal double bonds of bisACTHNGUTRNE(NGU allene)s, see: c) S.-K.
(allene)s: for Pd0-catalyzed [2+2] cycloaddition be-
ACHTUNGTRENNUNG
Kang, T.-G. Baik, A. N. Kulak, Y.-H. Ha, Y. Lim, J. Park, J. Am.
Chem. Soc. 2000, 122, 11529–11530; d) Y.-T. Hong, S.-K. Yoon, S.-
K. Kang, C.-M. Yu, Eur. J. Org. Chem. 2004, 4628–4635. See also
reference [8]. For Ni0-catalyzed intermolecular [2+2] cycloaddition
of allenes, see: S. Saito, K. Hirayama, C. Kabuto, Y. Yamamoto, J.
Am. Chem. Soc. 2000, 122, 10776–10780.
[9] a) S. Ma, P. Lu, L. Lu, H. Hou, J. Wei, Q. He, Z. Gu, X. Jiang, X.
Jin, Angew. Chem. 2005, 117, 5409–5412; Angew. Chem. Int. Ed.
2005, 44, 5275–5278; b) P. Lu, S. Ma, Org. Lett. 2007, 9, 5319–5321;
c) S. Ma, L. Lu, Chem. Asian J. 2007, 2, 199–204.
[23] Isomerization of 9ea to 9eb under the reaction conditions was not
observed. Both compounds 9ea and 9eb would be formed from 1,3-
diene intermediate 9e’ in the reaction of 8e.
[24] a) C. Nꢄjera, M. Yus, Tetrahedron 1999, 55, 10547–10658; b) N. S.
Simpkins, Sulphones in Organic Synthesis, Pergamon Press, Oxford,
1993.
[10] P. Lu, S. Ma, Org. Lett. 2007, 9, 2095–2097.
[11] a) W. Shu, G. Jia, S. Ma, Angew. Chem. 2009, 121, 2826–2829;
Angew. Chem. Int. Ed. 2009, 48, 2788–2791; b) Y. Deng, Y. Shi, S.
Ma, Org. Lett. 2009, 11, 1205–1208.
[12] a) S. M. Kim, J. H. Park, Y. K. Kang, Y. K. Chung, Angew. Chem.
2009, 121, 4602–4605; Angew. Chem. Int. Ed. 2009, 48, 4532–4535;
b) J. H. Park, E. Kim, H.-M. Kim, S. Y. Choi, Y. K. Chung, Chem.
Commun. 2008, 2388–2390.
[25] Y. Watanabe, Y. Ueno, T. Araki, T. Endo, M. Okawara, Tetrahedron
Lett. 1986, 27, 215–218.
[26] Other examples dealing with desulfonylation of our products, see:
a) N. Miyakoshi, Y. Ohgaki, K. Masui, C. Mukai, Heterocycles 2007,
74, 185–189; b) D. Aburano, F. Inagaki, S. Tomonaga, C. Mukai, J.
Org. Chem. 2009, 74, 5590–5594.
[13] a) C. Mukai, I. Nomura, K. Yamanishi, M. Hanaoka, Org. Lett.
2002, 4, 1755–1758; b) C. Mukai, I. Nomura, S. Kitagaki, J. Org.
Chem. 2003, 68, 1376–1385; c) C. Mukai, F. Inagaki, T. Yoshida, S.
Kitagaki, Tetrahedron Lett. 2004, 45, 4117–4121; d) C. Mukai, F. In-
5182
www.chemeurj.org
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2010, 16, 5173 – 5183

Cycloadditions and Cycloisomerizations of Bis(sulfonylallene)s
FULL PAPER
[27] For the [1,5]-sigmatropic hydrogen shift in 1,3-cyclooctadiene, see:
B. A. Hess, Jr., J. E. Baldwin, J. Org. Chem. 2002, 67, 6025–6033,
and references therein.
2002, 124, 15186–15187; b) T. Shibata, Y. Takesue, S. Kadowaki, K.
Takagi, Synlett 2003, 268–270; c) K. M. Brummond, B. Mitasev, Org.
Lett. 2004, 6, 2245–2248; d) K. M. Brummond, T. O. Painter, D. A.
Probst, B. Mitasev, Org. Lett. 2007, 9, 347–349; e) X. Jiang, S. Ma, J.
Am. Chem. Soc. 2007, 129, 11600–11607. See also references
[13c,d]. Allenenes: f) T. Makino, K. Itoh, Tetrahedron Lett. 2003, 44,
6335–6338; g) K. M. Brummond, H. Chen, B. Mitasev, A. D. Casar-
ez, Org. Lett. 2004, 6, 2161–2163. See also reference [6].
[28] Production of a tetraene derivative (3,4-dimethylene-1,5-hexadiene)
by thermolysis of bisACTHNUTRGNE(NUG allene)(1,2,6,7-octatetraene) in the gas phase
and in solution has been reported, see: a) L. Skattebøl, S. Solomon,
J. Am. Chem. Soc. 1965, 87, 4506–4513; b) W. R. Roth, G. Erker,
Angew. Chem. 1973, 85, 510–511; Angew. Chem. Int. Ed. Engl.
1973, 12, 503–504; c) W. Grimme, H.-J. Rother, Angew. Chem. 1973,
85, 512–514; Angew. Chem. Int. Ed. Engl. 1973, 12, 505–506.
[29] Eight- or nine-membered ring construction from acyclic substrates is
generally difficult due to entropic and enthalpic factors. See: G. Illu-
minati, L. Mandolini, Acc. Chem. Res. 1981, 14, 95–102.
[35] Our proposal is based on the fact that the [1,5]-H shift was observed
in the course of carbonylative [2+2+1] cycloaddition of decatet-
AHCTUNGTREGNUNrN aenes under similar conditions (under CO instead of N2 atmos-
phere). However, we cannot completely rule out the possibility of
ꢀ
other reaction pathways such as allylic C H activation/carbometal-
[30] For the medium-sized ring construction using allene functionality,
see: X. Jiang, Q. Yang, Y. Yu, C. Fu, S. Ma, Chem. Eur. J. 2009, 15,
7283–7286, and references therein.
lation/reductive elimination (references [6,34f,g]) and cyclometalla-
tion (formation of I)/b-elimination/reductive elimination sequence
(reference [10]), which have been suggested for the cycloisomeriza-
[31] For the metal-mediated synthesis of medium-sized rings, see: L. Yet,
Chem. Rev. 2000, 100, 2963–3008.
tion of allenenes and bis
the allene terminus.
ACHTUNGTRENNUNG
[32] J.-C. Choi, S. Sarai, T. Koizumi, K. Osakada, T. Yamamoto, Organo-
metallics 1998, 17, 2037–2045.
[36] The sequential thermal [2+2] cycloaddition/ACHTUNGTRENNUNG
zation reaction of 1,2,4Z,7-tetraenes has been reported by Ma
group, see: S. Ma, Z. Gu, J. Am. Chem. Soc. 2006, 128, 4942–4943.
[37] Neither compounds 15a nor 15a’ was converted into 27a in the
presence of RhI catalyst in toluene at 808C.
[33] Some metal-catalyzed enyne cycloisomerizations via metalocyclo-
pentene formation followed by reductive elimination (and cyclore-
version) have been reported, see: C. Aubert, O. Buisine, M. Malac-
ria, Chem. Rev. 2002, 102, 813–834.
[34] For the RhI-catalyzed cycloisomerization of allenes, see: allenynes:
a) K. M. Brummond, H. Chen, P. Sill, L. You, J. Am. Chem. Soc.
Received: December 29, 2009
Published online: March 25, 2010
Chem. Eur. J. 2010, 16, 5173 – 5183
ꢀ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
5183