Rh(I)-catalyzed intramolecular [2 + 2 + 1] cycloaddition of allenenes: Construction of bicyclo[4.3.0]nonenones with an angular methyl group and tricyclo[6.4.0.01,5]dodecenone

Article abstract of DOI:10.3762/bjoc.7.52

The [RhCl(CO)dppp]₂-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bi-cyclo[4.3.0] nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson-Kha

Full text of DOI:10.3762/bjoc.7.52

Rh(I)-catalyzed intramolecular [2 + 2 + 1]
cycloaddition of allenenes: Construction of
bicyclo[4.3.0]nonenones with an angular methyl
group and tricyclo[6.4.0.01,5]dodecenone
Fuyuhiko Inagaki, Naoya Itoh, Yujiro Hayashi, Yumi Matsui
and Chisato Mukai*
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2011, 7, 404–409.
Division of Pharmaceutical Sciences, Graduate School of Natural
Science and Technology, Kanazawa University, Kakuma-machi,
Kanazawa 920-1192, Japan
doi:10.3762/bjoc.7.52
Received: 19 January 2011
Accepted: 16 March 2011
Published: 07 April 2011
Email:
Chisato Mukai* - cmukai@kenroku.kanazawa-u.ac.jp
This article is part of the Thematic Series "Allene chemistry".
Guest Editor: K. M. Brummond
* Corresponding author
Keywords:
allene; bicyclo[4.3.0] derivatives; carbonylative [2 + 2 + 1]
cycloaddition; quaternary center construction; rhodium
© 2011 Inagaki et al; licensee Beilstein-Institut.
License and terms: see end of document.
Abstract
The [RhCl(CO)dppp]2-catalyzed intramolecular carbonylative [2 + 2 + 1] cycloaddition of allenenes was developed to prepare bi-
cyclo[4.3.0]nonenones possessing a methyl group at the ring junction, which is difficult to achieve by the Pauson–Khand reaction
of the corresponding enynes. This method also provided a new procedure for the construction of the tricyclo[6.4.0.01,5]dodecenone
framework in a satisfactory yield.
Introduction
The Co2(CO)8-mediated Pauson–Khand reaction (PKR) [1,2] is ciently afford 5-alkyl (or phenyl)bicyclo[3.3.0]oct-1-en-3-ones
well recognized as a formal [2 + 2 + 1] cycloaddition of three [10-19], the one-methylene homologated substrates furnish the
components, the alkyne π-bond, the alkene π-bond and carbon corresponding bicyclo[4.3.0] skeletons with an angular
monoxide (CO), for producing cyclopentenone derivatives. substituent in rather lower yields [20-22].
The intramolecular PKR [3-9] provides a powerful method
for the construction of bicyclo[3.3.0]oct-1-en-3-one and bi- Recent efforts in our laboratory have developed the
cyclo[4.3.0]non-1(9)-en-8-one frameworks. In contrast to the [RhCl(CO)2]2-catalyzed [2 + 2 + 1] cycloaddition of 3-phenyl-
fact that the 2-alkyl (or phenyl)-1-hepten-6-ynes also effi- sulfonyl-1,2,7-octatrienes and lead to bicyclo[4.3.0]non-1(9)-
404

Beilstein J. Org. Chem. 2011, 7, 404–409.
en-8-one derivatives, in which the distal double bond of the Results and Discussion
allenyl moiety serves exclusively as the π-component [23]. This In previous studies, we investigated the carbonylative
method could not only be applicable for the construction of the [2 + 2 + 1] cycloaddition reaction of two allenenes 1 and 4 with
larger bicyclo[5.3.0]dec-1(10)-en-9-one skeleton, but also either a SO2Ph or CO2Me substituent on the proximal double
provides a new entry for the preparation of three types of trans- bond of the allene group in the presence of several Rh(I) cata-
2-phenylsulfonylbicyclo[4.3.0]non-1(9)-en-8-one derivatives lysts ([RhCl(CO)2]2, [RhCO(dppp)2]Cl or [RhCl(CO)dppp]2).
2a–c in moderate to high yields with an alkyl group (Me, We have now examined the similar ring-closing reaction using
(CH2)2OMe) at the ring junction from 7-alkyl-3-phenylsul- an alternative allenene 7a with a methyl group on the allenyl
fonyl-1,2,7-octatrienes 1a–c. The formation of 2 can be ratio- group for further evaluation of these reactions. According to the
nalized by the initial formation of the 6-alkyl-2-phenylsulfonyl- conditions described for the formation of 2, a solution of 7a in
bicyclo[4.3.0]non-1-en-8-one derivative 3, followed by subse- toluene was heated at 120 °C for 4 h in the presence of 5 mol %
quent isomerization to the α,β-unsaturated ketones 2. By taking of [RhCl(CO)2]2 under 5 atm of CO to afford the desired 4,4-
advangage of this newly developed reaction, we have bis(methoxycarbonyl)-2,6-dimethylbicyclo[4.3.0]non-1-en-8-
completed the first total syntheses of two tricyclic sesquiter- one (8a) in 38% yield (Table 1, entry 1). A similar reaction
penes 6a,b, isolated from Jatropha neopauciflora, from the under 1 atm of CO gave 8a in a better yield (Table 1, entry 2).
methoxycarbonylallenene 4 via the bicyclo[4.3.0]nonenone These results are in sharp contrast to the previous findings,
derivative 5 [24]. The key step in these total syntheses was where increasing the CO pressure from 1 to 5 atm led to an
carried out as follows: The allenene 4, derived from D-tartrate, improvement in the chemical yield (see reference [23],
was heated under reflux in the presence of 10 mol % of Table 1). The alternative condition ([RhCO(dppp)2]Cl
[RhCO(dppp)2]Cl [25] under a CO atmosphere to produce (10 mol %) under a CO atmosphere) provided the ring-closing
exclusively the bicyclo[4.3.0]derivative 5 with the desired product 8a in 75% yield (Table 1, entry 3). It has already been
stereochemistry in 74% yield (Scheme 1). Our continuous shown that the Rh(I)-catalyzed Pauson–Khand type reaction
interest in this field prompted us to optimize the reaction (PKTR) of enynes under a low CO pressure [26,27] leads to
conditions in order to make our method more useful. better results. Thus, the ring-closing reaction of 7a was
This paper describes the Rh(I)-catalyzed [2 + 2 + 1] cyclo- performed under an atmosphere consisting of 0.2 atm of CO
addition of allenenes for the facile preparation of and 0.8 atm of Ar, or of 0.05 atm of CO and 0.95 atm of Ar to
the bicyclo[4.3.0]nonenone derivatives possessing an produce 8a in 71% and 74% yields, respectively (Table 1,
angular methyl group, and for the construction of the entries 4 and 5). Next, the reaction with [RhCl(CO)dppp]2 in
tricyclo[6.4.0.01,5]dodecenone skeleton.
the presence or absence of a silver salt [27-34] was examined
Scheme 1: Rh(I)-catalyzed Pauson–Khand type reaction of 1 and 4.
405

Beilstein J. Org. Chem. 2011, 7, 404–409.
Table 1: Rh(I)-catalyzed PKTR of 7a.
entry
Rh(I) cat. (mol %)
additive (mol %)
CO (atm)
time (h)
yield of 8a (%)
1
[RhCl(CO)2]2 (5)
—
5
4
38
54
75b
71
74
68
79
88
51f
78
93
79
84
2
[RhCl(CO)2]2 (5)
—
1
16
17
17
6
3
[RhCO(dppp)2]Cl (10)
[RhCO(dppp)2]Cl (10)
[RhCO(dppp)2]Cl (10)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
[RhCl(CO)dppp]2 (5)
—
1
4
—
0.2c
0.05d
1
5
—
6
—
19
11
7
7
—
0.2c
0.1e
0.05d
0.1e
0.05d
0.05d
0.05d
8
—
9
—
8
10
11
12
13
AgBF4 (12)
AgBF4 (12)
AgSbF6 (12)
AgCl (12)
1.5
1.5
1.5
6
aBath temperature. b8a was obtained in 18% yield under 5 atm of CO. cThe reaction was conducted under 0.2 atm of CO and 0.8 atm of Ar. dThe
reaction was conducted under 0.05 atm of CO and 0.95 atm of Ar. eThe reaction was conducted under 0.1 atm of CO and 0.9 atm of Ar. fCompound
9a was obtained in 31%.
(Table 1, entries 6–13). A significant improvement (8a, 93%) interfere with the ring-closing reaction and afforded 9e in 63%
was observed when the ring-closing reaction of 7a was carried yield (Table 2, entry 6). On the other hand, 7f provided the
out in the presence of 5 mol % of [RhCl(CO)dppp]2 and oxabicyclic derivative 9f in a low yield (Table 2, entry 7). The
12 mol % of AgBF4 under an atmosphere consisting of 0.05 geminal disubstituent effect (Thorpe–Ingold-type effect) of 1a
atm of CO and 0.95 atm of Ar at 120 °C (Table 1, entry 11). and 7a might be responsible for the high yields of the ring-
Almost all of the reactions gave 2,6-dimethylbicyclo[4.3.0]non- closed products.
1-en-8-one 8a, and the α,β-unsaturated ketone 9a could not be
detected except for entry 9. This observation obviously differs The Rh(I)-catalyzed PKTR of the non-substituted allenene 7g
from the PKTR products 2 and 5 having an electron with- was investigated as a control experiment under the several
drawing group instead of a methyl group (Scheme 1).
conditions (e.g., conditions of entries 3, 6, 10 and 11 in Table 1)
but resulted in the formation of the intractable mixtures
We next investigated the scope of this Rh(I)-catalyzed PKTR (Scheme 2). These results in combination with the successful
using several substrates under the condition of entry 11 in examples shown in Table 2 indicated that the substituent on the
Table 1. The nitrogen congener 7b produced the corresponding proximal double bond of the allene might be mandatory.
azabicyclic compound 8b in 56% yield, although a prolonged Removal of the allylic sulfone group in 2a was achieved by
reaction time was required (Table 2, entry 1). The sulfonyl- tributyltin hydride in the presence of AIBN to give 9g in 91%
allenene 7c, which has a simple methylene tether, provided the yield [35-41]. Thus, the phenylsulfonyl group of 2a can be
cyclopentenone derivative 9c in 55% yield as expected from the regarded as a hydrogen surrogate and this procedure provides a
results given in Scheme 1 (Table 2, entry 2). As noted above, new method for the preparation of 9g.
compounds 2a,b could be obtained in the presence of
[RhCl(CO)2]2: [RhCl(CO)dppp]2 also worked as well as the The intramolecular Rh(I)-catalyzed PKTR of allenenes is
previous conditions (Table 2, entries 3 and 4). The oxygen applicable to the more complex substrate as shown in Table 3
congener 7d produced the corresponding oxabicyclic com- [42-44]. Exposure of the cyclopentene 10 to the standard
pound 9d in 49% yield (Table 2, entry 5). The methoxy- conditions in Table 2 did not lead to the desired
carbonyl functionality on the allenyl moiety 7e was found not to tricyclo[6.4.0.01,5]dodec-7-en-6-one 11, instead the
406

Beilstein J. Org. Chem. 2011, 7, 404–409.
Table 2: Rh(I)-catalyzed PKTR of 7-methyl-1,2,7-trienes.
entry
1
allenene
product
time (h)
yield (%)
56
6.5
2
3
3
55
1
88a,b
4
5
2
3
66
49
6
7
5
63
22
4.5
aThe reaction was carried out without AgBF4 under a CO atmosphere. b2a was obtained in 68% yield in the presence of 12 mol % of AgBF4.
spiro[4.5]deca-1,6-diene derivative 12 was formed exclusively The [RhCl(CO)dppp]2-catalyzed reaction of 10 under a N2
in 87% yield (Table 3, entry 1). After screening several reaction atmosphere with or without AgBF4 produced the spiro product
conditions, the tricyclic derivative 11 was obtained in 73% yield 12 in 93% and 91% yield, respectively, whereas no spiro prod-
along with 12 (24%) when the reaction was carried out in the uct 12 was obtained under thermal conditions without a Rh(I)-
absence of AgBF4 under a CO atmosphere (Table 3, entry 2). catalyst (Table 3, entries 3–5). Therefore, the formation of 12
407

Beilstein J. Org. Chem. 2011, 7, 404–409.
Supporting Information
Full experimental details, compound characterization data,
1H NMR spectra and 13C NMR spectra for all new
compounds described.
Supporting Information File 1
Experimental, characterization data and spectra.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-7-52-S1.pdf]
Acknowledgements
This work was supported in part by a Grant-in Aid for Scien-
tific Research from the Ministry of Education, Culture, Sports,
Science, and Technology, Japan, for which we are thankful.
Scheme 2: Formation of 4,4-bis(methoxycarbonyl)-6-
methylbicyclo[4.3.0]non-1(9)-en-8-one (9g).
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