Ruthenium-catalyzed cyclic carbonylation of allenyl alcohols. Selective synthesis of γ- and δ-lactones

Article abstract of DOI:10.1021/ol990377d

(Formula presented) Ruthenium complex-catalyzed carbonylation of allenyl alcohols quantitatively gave cyclic carbonyl compounds, γ- and δ-lactones, in which the hydroxy group of allenyl alcohols participated in the cyclization. A wide variety of allenyl alcohols, such as mono-, di-, and trisubstituted alcohols, can be used in this reaction to produce 3- and 4-substituted γ-lactones. Similarly, the cyclic carbonylation of 3,4-pentadien-1-ol 10a and 2-methyl-4,5-hexadien-2-ol 11a gave δ-lactones, 5,6-dihydro-3-methyl-2H-pyran-2-one 10b, and 5,6-dihydro-6,6-dimethyl-3-methyl-2H-pyran-2-one 11b, respectively, in a quantitative yield.

Full text of DOI:10.1021/ol990377d

ORGANIC
LETTERS
2
000
Vol. 2, No. 4
41-443
Ruthenium-Catalyzed Cyclic
Carbonylation of Allenyl Alcohols.
Selective Synthesis of γ- and
δ-Lactones
4
Eiji Yoneda, Takayuki Kaneko, Shi-Wei Zhang, Kiyotaka Onitsuka, and
Shigetoshi Takahashi*
The Institute of Scientific and Industrial Research, Osaka UniVersity, Mihogaoka,
Ibaraki, Osaka 567-0047, Japan
takahashi@sanken.osaka-u.ac.jp
Received November 29, 1999
ABSTRACT
Ruthenium complex-catalyzed carbonylation of allenyl alcohols quantitatively gave cyclic carbonyl compounds, γ- and δ-lactones, in which
the hydroxy group of allenyl alcohols participated in the cyclization. A wide variety of allenyl alcohols, such as mono-, di-, and trisubstituted
alcohols, can be used in this reaction to produce 3- and 4-substituted γ-lactones. Similarly, the cyclic carbonylation of 3,4-pentadien-1-ol 10a
and 2-methyl-4,5-hexadien-2-ol 11a gave δ-lactones, 5,6-dihydro-3-methyl-2H-pyran-2-one 10b, and 5,6-dihydro-6,6-dimethyl-3-methyl-2H-pyran-
2-one 11b, respectively, in a quantitative yield.
Much attention is being devoted to tandem carbonylation
reactions of alkenes and alkynes catalyzed by transition-metal
complexes in terms of the efficient syntheses of heterocyclic
Scheme 1
1
compounds such as lactones and lactams. In such tandem
carbonylation reactions, unsaturated substrates having a
functional group adjacent to the CdC or CtC bond initially
coordinate to metal catalysts ([M]) to give intermediate A.
Intramolecular interaction of the metal with the functional
2
3
4
5
groups such as hydroxyl, amino, formyl, and ester results
in the formation of metallacycle intermediate B, followed
by insertion of carbon monoxide and then elimination of the
metal to afford cyclic carbonyl compound C (Scheme 1).
Among heterocyclic products from this type of tandem
carbonylation, particularly γ-lactone is an important precursor
for the synthesis of many natural and biologically active
compounds. Actually, the tandem reactions of alkenes and
alkynes giving γ-lactones have been extensively studied,2
6
whereas there are few examples of the cyclic carbonylation
7
of allenes that have been investigated. Very recently, Ma
(1) For a review, see: (a) Schore N. E. Chem. ReV. 1988, 88, 1081. (b)
and co-workers have reported a synthetic method for
γ-lactones by a Pd(0)-catalyzed intramolecular cyclization
reaction of 2,3-allenecarboxylic acids with aryl or alkenyl
halides, but the reaction gave γ-lactones in low yields.8
Herein, we wish to report a new type of the tandem reaction
Colquhoun, H. M.; Thompson, D. J.; Twigg, M. V. Carbonylation: Direct
Synthesis of carbonyl Compounds; Plenum Press: New York, 1991. (c)
Stille, J. K. In ComprehensiVe Organic Synthesis; Trost, B. M., Fleming,
I., Eds.; Pergamon Press: New York, 1991; Vol. 4, p 913. (d) Ojima, I.;
Tzamarioudaki, M.; Li, Z.; Donovan, R. J. Chem. ReV. 1996, 96, 635. (e)
Ungvary, F. Coord. Chem. ReV. 1998, 170, 245.
1
0.1021/ol990377d CCC: $19.00 © 2000 American Chemical Society
Published on Web 02/04/2000

of allenyl alcohols with carbon monoxide using a ruthenium
complex as a catalyst. This carbonylation of allenyl alcohols
directly gives γ- and δ-lactones in excellent yields. Although
there are some examples on carbonylation of allenes leading
Table 1. Carbonylation of Allenyl Alcoholsa
9
to unsaturated carboxylic acids, to our knowledge, the
present reaction is the first catalytic cyclocarbonylation of
allenyl alcohols.
A representative reaction procedure is as follows. A
mixture of 1-propa-1,2-dienylcyclohexan-1-ol 1a (1 mmol),
3 3
Ru (CO)12 (0.01 mmol), and Et N (1.5 mmol) in 1,4-dioxane
(15 mL) was stirred at 100 °C for 8 h under 10 atm of carbon
monoxide (eq 1). The gas chromatographic analysis of the
reaction mixture showed that the carbonylation reaction
selectively yielded a sole product. Simple removal of the
catalyst by silica gel column chromatography gave 3-methyl-
1
-oxaspiro[4.5]dec-3-en-2-one 1b in 99% yield, which was
1
13
identified by the H NMR, C NMR, IR, and mass spectra.
The formation of any other products was not recognized in
the H NMR and C NMR. When the reaction was carried
1
13
out at lower temperature (50 °C), 1b was obtained only in
17% yield, and 80% of starting substrate 1a was recovered.
When the reaction temperature was increased to 80 °C, the
reaction gave 1b in 75% yield, and 20% of 1a was recovered.
Even under atmospheric pressure of carbon monoxide, the
carbonylation took place at 100 °C to give 1b, though the
(2) (a) Urata, H.; Yugari, H.; Fuchikami, T. Chem. Lett. 1987, 833. (b)
Ohe, K.; Takahashi, H.; Uemura, S.; Sugita, N. J. Org. Chem. 1987, 52,
4
6
859. (c) Matsuda, I.; Ogiso, A.; Sato, S. J. Am. Chem. Soc. 1990, 112,
120. (d) Ali, E. B.; Alper, H. J. Org. Chem. 1991, 56, 5357. (e) Matsushita,
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4
264. (g) Xiao, W.; Alper, H. J. Org. Chem. 1997, 62, 3422. (h) Yu, W.;
Alper, H. J. Org. Chem. 1997, 62, 5684. (i) Gabriele, B.; Salerno, G.; De
Pascali, F.; Costa, M. Chiusoli, G. P. J. Chem. Soc., Perkin Trans. 1 1997,
1
47. (j) Ogawa, A.; Kawabe, K.; Kawakami, J.; Mihara, M.; Hirao, T.;
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Hirao, K.; Zhang, S.; Takahashi, S. J. Chem. Soc., Perkin Trans. 1 1998,
4
77. (l) Yoneda, E.; Kaneko, T.; Zhang, S.; Takahashi, S. Tetrahedron Lett.
1998, 39, 5061. (m) Zhang, X.; Cao, P. J. Am. Chem. Soc. 1999, 121, 7708.
(
3) (a) Matsuda, I.; Sakakibara, J.; Nagashima, H. Tetrahedron Lett. 1991,
3
1
1
2, 7431. (b) Hirao, K.; Morii, K.; Joh, T. Takahashi, S. Tetrahedron Lett.
995, 36, 6243. (c) Delgado, R. A.; Rosa, R. G.; Mavarez, E. J. Mol. Catal.
996, 108, 125. (d) Bacchi, A.; Chiusoli, G. P.; Costa, M.; Gabriele, B.;
Righi, C.; Salerno, G. J. Chem. Soc., Chem. Commun. 1997, 1209.
4) (a) Ojima, I.; Tzamarioudaki, M.; Tsai, C. J. Am. Chem. Soc. 1994,
16, 3643. (b) Sugioka, T.; Zhang, S.; Morii, N.; Joh, T.; Takahashi, S.
Chem. Lett. 1996, 249.
5) (a) Kudo, K.; Oida, Y.; Mitsuhashi, K.; Mori, S.; Komatsu, K.; Sugita,
a
Reaction conditions: substrate (1 mmol), NEt3 (1.5 mmol), CO (initial
(
pressure 10 atm at 25 °C), Ru3(CO)12 (0.01 mmol) in doxane (15 ml) at
1
00 °C for 8 h in a 100 mL stainless autoclave. b Isolated yield.
1
(
N. Bull. Chem. Soc. Jpn. 1996, 69, 1337. (b) Sugioka, T. Yoneda, E.;
Onitsuka, K.; Zhang, S.; Takahashi, S. Tetrahedron Lett. 1998, 38, 4989.
yield decreased to 62%. As the catalyst for the present
carbonylation, ruthenium complexes such as RuCl ‚xH O and
RuCl (PPh showed a definite activity to give 1b in 82 and
41% yield, respectively; however, RuCl (dppe) is inactive.
Complexes such as Co (CO) , Fe (CO)10, and Rh (CO)16 are
not effective for the present reaction. In an investigation on
the effect of additives, the lack of Et N reduced the yield of
b to 62% yield. On the basis of the above results, the
(
6) (a) Nakanishi, K.; Goto, T.; Ito, S. Natural Product Chemistry;
Kodansya: Tokyo, 1974; Vols. 1-3. (b) Dictionary of Natural Products,
st ed.; Buckingham, J., Ed.; Chapman & Hall: New York. 1994.
7) (a) The Chemistry of Ketenes, Allenes, and Related Compounds; Patai,
3
2
2
3 3
)
1
(
2
2
S., Ed.; John Wiley & Sons: New York, 1980; Part 1. (b) Schuster, H. F.;
Coppola, G. M. Allenes in Organic Synthesis; John Wiley & Sons: New
York, 1988.
2
8
2
6
(
8) Ma, S.; Shi, Z.; J. Org. Chem. 1998, 63, 6387.
3
(9) (a) Satyanarayana, N.; Alper, H.; Amer, I. Organometallics 1990, 9,
1
2
84. (b) Piotti, M. E.; Alper, H. J. Am. Chem. Soc. 1994, 59, 1956. (c)
Xiao, W.-J.; Giuseppe, V.; Alper, H. J. Org. Chem. 1998, 63, 2609.
carbonylation of several allenyl alcohols was examined under
442
Org. Lett., Vol. 2, No. 4, 2000

the following conditions: substrate (1 mmol); catalyst, Ru
CO)12 (1 mol %); additive, Et N (1.5 mmol); solvent,
dioxane (15 mL), CO 10 atm, 100 °C.
The results obtained are summarized in Table 1.10 The
cyclic carbonylations of allenyl alcohols in Table 1 proceeded
smoothly to give the corresponding γ- or δ-lactones in
excellent yields. For example, the reaction of 1,1-disubsti-
tuted 2,3-allenyl alcohol 2a gave the corresponding γ-lactone,
3
-
9b, quantitatively (run 9). Furthermore, the cyclic carbonyl-
ation of 10a and 11a, which contain a dimethylene spacer
between the hydroxyl and allenyl groups, similarly took place
to give δ-lactones 10b and 11b in 95 and 98% yield,
respectively (runs 10 and 11).
In conclusion, we have found that ruthenium complexes
catalyze the novel cyclic carbonylation of allenyl alcohols
to give lactones with a high selectivity. This intramolecular
tandem reaction provides a new and efficient method for the
selective synthesis of γ- and δ-lactones simply from allenyl
alcohols with carbon monoxide.
(
3
2
b, with a high selectivity (run 2). 2,3-Allenyl alcohols 3a
and 4a, which have an alkyl or an aryl substituent at the
-position of allenyl alcohols, gave the corresponding
γ-lactones, 3b and 4b, in quantitative yields (runs 3 and 4).
-Methoxy-2,3-allenyl alcohols such as 5a, 6a, 7a, and 8a
gave tri- or tetrasubstituted-γ-lactones 5b, 6b, 7b, and 8b
runs 5-8). These compounds cannot be prepared by the
cyclic carbonylation of propargyl alcohols using a Pd
1
Acknowledgment. We thank the technical staff in the
Material Analysis Center of ISIR, Osaka University, for mass
spectrometric and elemental analyses. E.Y. is grateful for a
JSPS Fellowship for Japan Junior Scientists
2
(
2
h
catalyst. The cyclic carbonylation of 9a, which is a
trisubstituted allene, also gave the corresponding γ-lactone,
Supporting Information Available: Experimental de-
tails. This material is available free of charge via the Internet
at http://pubs.acs.org.
(10) All new compounds were identified by NMR, IR, mass spectral
analyses, and elemental analyses. See the Supporting Information.
OL990377D
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