Doyle-kirmse reaction of allylic sulfides with diazoalkane-free (2-furyl)carbenoid transfer

Article abstract of DOI:10.1021/ol034731q

(Matrix presented) In the presence of rhodium catalyst, (2-furyl) carbenoids generated from conjugated ene-yne-carbonyl compounds 1 efficiently undergo carbene transfer reactions with allylic sulfides followed by [2,3]sigmatropic rearrangement of sulfur y

Full text of DOI:10.1021/ol034731q

ORGANIC
LETTERS
2003
Vol. 5, No. 15
2619-2621
Doyle−Kirmse Reaction of Allylic
Sulfides with Diazoalkane-Free
(2-Furyl)carbenoid Transfer
Yumiko Kato, Koji Miki, Fumiaki Nishino, Kouichi Ohe,* and Sakae Uemura*
Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering,
Kyoto UniVersity, Sakyo-ku, Kyoto 606-8501, Japan
ohe@scl.kyoto-u.ac.jp; uemura@scl.kyoto-u.ac.jp
Received May 1, 2003
ABSTRACT
In the presence of rhodium catalyst, (2-furyl)carbenoids generated from conjugated ene-yne-carbonyl compounds 1 efficiently undergo carbene
transfer reactions with allylic sulfides followed by [2,3]sigmatropic rearrangement of sulfur ylides to give furan-containing sulfides in good
yields. When diallyl sulfide is employed, heteroatom-containing polycyclic compounds are obtained by sequential intramolecular Diels−Alder
cyclization reaction with a constructed furan ring as an enophile.
The Doyle-Kirmse reaction of allylic sulfides and diazo
compounds ([2,3]sigmatropic rearrangement of sulfur ylides)
Scheme 1
is a powerful synthetic method for creating new C-C
bonds.1,2 The reaction presumably involves carbenoid com-
plexes as intermediates. We report herein the rhodium(II)-
catalyzed Doyle-Kirmse-type reaction using (2-furyl)-
carbenoid precursors 1 without involving the corresponding
diazoalkanes, as shown in Scheme 1. We have already
(1) For reviews, see: (a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern
Catalytic Methods for Organic Synthesis with Diazo Compounds: From
Cyclopropanes to Ylides; John Wiley&Sons: New York, 1998. (b) Li, A.-
H.; Dai, L.-X.; Aggarwal, V. K. Chem. ReV. 1997, 97, 2341. (c) Doyle, M.
reported the cyclopropanation of alkenes via (2-furyl)-
P. In ComprehensiVe Organometallic Chemistry II; Hegedus, L. S., Ed.;
carbenoid complexes 2a generated from 1a, which can be
catalyzed by a wide range of transition metal complexes
(Scheme 2).3,4 The following investigation demonstrates the
efficacy of electron-withdrawing groups introduced at the
R1 position of 1, as well as catalysis by a rhodium(II)
Pergamon: Oxford, 1995; Vol. 12, pp 421-468.
(2) For leading references, see: (a) Zhang, X.; Qu, Z.; Ma, Z.; Shi, W.;
Jin, X.; Wang, J. J. Org. Chem. 2002, 67, 5621. (b) Simonneaux, G.;
Galardon, E.; Paul-Roth, C.; Gulea, M.; Masson, S. J. Organomet. Chem.
2001, 617-618, 360. (c) Carter, D. S.; Van Vranken, D. L. Org. Lett. 2000,
2, 1303. (d) Carter, D. S.; Van Vranken, D. L. Tetrahedron Lett. 1999, 40,
1617. (e) Aggarwal, V. K.; Ferrara, M.; Hainz, R.; Spey, S. E. Tetrahedron
Lett. 1999, 40, 8923. (f) Gulea, M.; Marchand, P.; Masson, S.; Saquet, M.;
Collignon, N. Synthesis 1998, 1635. (g) Meyer, O.; Cagle, P. C.; Weickhardt,
K.; Vichard, D.; Gladysz, J. A. Pure Appl. Chem. 1996, 68, 79. (h) Cagle,
P. C.; Arif, A. M.; Gladysz, J. A. J. Am. Chem. Soc. 1994, 117, 3655. (i)
Doyle, M. P.; Tamblyn, W. H.; Bagheri, V. J. Org. Chem. 1981, 46, 5094.
(j) Kirmse, W.; Kapps, M. Chem. Ber. 1968, 101, 994.
(3) Miki, K.; Nishino, F.; Ohe, K.; Uemura, S. J. Am. Chem. Soc. 2002,
124, 5260. For isolation of chromium (2-furyl)carbenoid, see: Miki, K.;
Yokoi, T.; Nishino, F.; Ohe, K.; Uemura, S. J. Organomet. Chem. 2002,
645, 228. For vinylcarbenoids as related carbenoid species, see: Miki, K.;
Ohe, K.; Uemura, S. Tetrahedron Lett. 2003, 44, 2019.
10.1021/ol034731q CCC: $25.00 © 2003 American Chemical Society
Published on Web 06/24/2003

Diazoalkane-free carbenoid transfer reaction using 1 was also
effective for more nucleophilic allyl methyl sulfide 6.2b,f
These results are summarized in Table 2. The reaction of 6
Scheme 2
Table 2. Rh-Catalyzed Carbene Transfer Reaction with Sulfide
6a
complex for the Doyle-Kirmse reaction of allylic sulfides.
When the Doyle-Kirmse reaction was carried out with
newly prepared 1b-d as carbenoid precursors in the presence
of [Rh(OAc)2]2 as a catalyst, the reaction was found to
proceed more efficiently than with 1a.
First, the reactions of 1 with allyl phenyl sulfide 3 as a
carbenoid acceptor were examined. Results are shown in
Table 1. The reaction of 1a with 3 in the presence of 2.5
entry
1
R1
R2
time (h)
isolated yield
1
2
3
4
1a
1b
1c
1d
H
Ph
H
H
7
120
48
60%
77%b
72%
91%
Bz
Ac
CO2Me
H
48
a Reaction conditions: 1 (0.25 mmol), sulfide 6 (2.5 mmol), [Rh(OAc)2]2
(0.006 mmol) in CH2Cl2 (1 mL) at reflux temperature. b 1b (11%) was
recovered.
Table 1. Rh-Catalyzed Carbene Transfer Reaction with Sulfide
3a
using 1a, which gave an unsatisfactory result with 3, afforded
the corresponding expected product 7a in 60% yield (entry1).
Reactions of 1b-d with sulfide 6 also gave products 7b-d
in fair to good yields, respectively, although prolonged
reaction periods (48-120 h) were required for each reaction
(entries 2-4).
Next, we carried out the rhodium-catalyzed reaction of 1
with diallyl sulfide 8. Results are shown in Table 3. The
reaction of 1a with 8 in refluxing CH2Cl2 gave the product
9a, in which the reaction occurred at one end of two allylic
moieties (entry 1). On the other hand, the reaction using 1b
under the same conditions produced 9b in 32% yield together
with tetracyclic product 10b in 43% yield as a mixture of
two isomers (ratio ) 79/21)6 (entry 2). The latter product
10b was considered as the subsequent intramolecular Diels-
Alder product from an initially produced 9b. Prolonging the
reaction time did not affect the product ratio of 9b and 10b,
but carrying out the reaction at 80 °C in 1,2-dichloroethane
entry
1
R1
R2
time (h)
isolated yield
1
2
3
4
1a
1b
1c
1d
H
Ph
H
H
4
10
7
complex mixture
Bz
Ac
CO2Me
98%
94%
83%
H
12
a Reaction conditions: 1 (0.25 mmol), sulfide 3 (2.5 mmol), [Rh(OAc)2]2
(0.006 mmol) in CH2Cl2 (1 mL) at reflux temperature.
mol % of [Rh(OAc)2]2 at room temperature or under
refluxing conditions gave a complex mixture, but none of
the desired product was obtained (entry 1). Thus, we next
examined the reaction of 3 using ene-yne-carbonyl com-
pounds 1b-d having electron-withdrawing groups at the R1
position, which could be expected to enhance the electro-
philicity of the intermediary carbenoid species to the sulfur
atom. The reaction of benzoyl group containing ene-yne-
carbonyl compound 1b with 3 gave 4b quantitatively (entry
2). Ene-yne-carbonyl compounds 1c and 1d, having acetyl
or methoxycarbonyl moiety, also reacted with 3 to give 4c
and 4d5 in good yields (entries 3 and 4). Since slow addition
of diazoalkane is necessary in most cases of Doyle-Kirmse
reaction using diazoalkanes,2 it is noted that slow addition
of 1 is not required in the present diazoalkane-free reaction.
(5) The isolated product 4d was thermally labile, which gradually
isomerized to another structural form 5d at ambient temperature. Although
the precise isomerism of 4d is not clear at present, [3,5]sigmatropic
rearrangement of an allylic moiety is a likely process for the isomerization.
For precedents of [3,5]sigmatropic rearrangement, see: Battye, P. J.; Jones,
D. W. J. Chem. Soc., Chem. Commun. 1986, 1807 and references therein.
(6) Two isomers stemmed from epimers at quaternary carbon having R1
and allyl groups of tetrahydrothiophene, although the configuration is not
yet clear. The intramolecular Diels-Alder reaction involving furan moieties
as enophiles might take place via exo-cyclization. Similar stereochemical
outcomes in the intramolecular Diels-Alder reactions have already been
reported: Klein, L. L. J. Am. Chem. Soc. 1985, 107, 2573. Klein, L. L.;
Shanklin, M. S. J. Org. Chem. 1988, 53, 5202. Sternbach, D. D.; Rossana,
D. M. J. Am. Chem. Soc. 1982, 104, 5853.
(4) For rhodium-catalyzed (2-pyrrolyl)carbenoid transferred cyclopro-
panation using ene-yne-imino ethers, see the immediately following
Letter: Nishino, F.; Miki, K.; Kato, Y.; Ohe, K.; Uemura, S. Org. Lett.
2003, 5, 2615.
2620
Org. Lett., Vol. 5, No. 15, 2003

and 12d as a single diastereomer, in 99% and 93% yields,
respectively (Scheme 3). These results clearly indicate that
Table 3. Rh-Catalyzed Carbene Transfer Reaction and
Sequential Diels-Alder Reaction with 8a
Scheme 3
isolated yield
time
entry
1
R1
R2 solvent temp (h)
9
10b
the rearrangement of sulfur ylides generated by (2-furyl)-
carbenoid transfer proceeds via [2,3]sigmatropy accepted for
Doyle-Kirmse reaction.
1
1a
1b Bz
1b Bz
1c Ac
H
Ph CH2Cl2 reflux
7
43%
-
2c
H
H
H
H
CH2Cl2 reflux 120 32% 43% (79/21)
DCEd 80 °C
DCEd 80 °C
3
4
5
72
54
-
-
92% (79/21)
80% (67/33)
In summary, we have demonstrated catalytic carbene
transfer reactions with allylic sulfides leading to ylide
formation on the basis of the in situ generation of (2-furyl)-
carbenoids from conjugated ene-yne-carbonyl compound.
The resulting sulfur ylides efficiently undergo [2,3]sigmat-
ropic rearrangement to give furan-containing sulfides. A
reaction cascade of [2,3]sigmatropy followed by intra-
molecular Diels-Alder reaction employing diallyl sulfide
allows the one-pot synthesis of polycyclic heterocycles.
1d CO2Me
CH2Cl2 reflux 120 trace 90% (73/27)
a Reaction conditions: 1 (0.25 mmol), sulfide 8 (2.5 mmol), [Rh(OAc)2]2
(0.006 mmol) in CH2Cl2 (1 mL). b The values in the parentheses indicate
diastereomeric ratio determined by 1H NMR. c 1b (9%) was recovered.
d DCE ) ClCH2CH2Cl.
(DCE) considerably improved the yield of the Diels-Alder
adduct 10b (entry 3). The absence of Diels-Alder adduct
10a in the reaction using 1a might be attributed to the lack
of the sterically demanding R1 group. In reactions of 1c and
1d with 8, Diels-Alder adducts 10c and 10d were obtained
with complete selectivity, respectively (entries 4 and 5).
Notably, in the reaction using 1d, reflux temperature in CH2-
Cl2 was sufficient for the Doyle-Kirmse-type reaction and
subsequent intramolecular Diels-Alder reaction. This clearly
shows that introduction of an electron-withdrawing meth-
oxycarbonyl moiety into 1 prominently facilitates intra-
molecular Diels-Alder reaction as well as ylide formation
by carbenoid transfer.
Acknowledgment. This work was supported by a Grant-
in-Aid for 21st Century COE program of a United Approach
to New Materials Science from the Ministry of Education,
Culture, Sports, Science, and Technology. Financial support
by Scientific Research (B) (no. 14350468) and Priority Areas
(A) “Exploitation of Multi-Element Cyclic Molecules” from
the Japan Society for the Promotion of Science is gratefully
acknowledged.
Supporting Information Available: Full experimantal
details and spectral data for all transformations and com-
pounds are described. This material is available free of charge
via the Internet at http://pubs.acs.org.
Finally, the reaction with cinnamyl phenyl sulfide 11 using
1 as a carbenoid source was examined in order to elucidate
the reaction pathway. In the presence of 2.5 mol %
[Rh(OAc)2]2, the reactions of 1b and 1d with 11 gave 12b
OL034731Q
Org. Lett., Vol. 5, No. 15, 2003
2621