C O M M U N I C A T I O N S
Table 1. Carbonylation of â-Lactones
in Science and Engineering and an Arnold and Mabel Beckman
Foundation Young Investigator Award, as well as funding from
the NSF (CHE-0243605). This material is based upon work
supported, in part, by the U.S. Army Research Laboratory and the
U.S. Army Research Office under grant no. DAAD19-02-1-0275
Macromolecular Architecture for Performance (MAP) MURI.
entry
R
R′
T (°C)
lactone/catalysta
yieldb (%)
1
H
Me
80
80
55
50
80
80
80
80
80
24
220
180
110
50
120
50
50
20
20
300
95
95
94
96
93
>99
90
97
90
Supporting Information Available: General experimental proce-
dures, spectral data for all new compounds, and X-ray data for 4 (PDF).
This material is available free of charge via the Internet at http://
pubs.acs.org.
2c
3d
4
H
H
Me
H
H
H
H
H
H
(R)-Mee
(R)-Mee
cis-Me
Et
(CH2)9CH3
CH2OnBu
CH2OSi(tBu)Me2
(CH2)2CHdCH2
H
5
6
7
8
9
10
References
(1) For selected uses of succinic anhydrides in small molecule and polymer
synthesis, see: Arason, K. M.; Bergmeier, S. C. Org. Prep. Proc. Int.
2002, 34, 339-366.
98
(2) For selected uses of succinic anhydrides as acylating agents, see: (a)
Nestaas, E.; Hrebenar, K. R.; Lewis, J. M.; Whitesides, G. M. (Emulsan
Biotechnologies, Inc., USA). U.S. Pat. US 5212235; Chem. Abstr. 1993,
119, 90809. (b) Shalaby, S. W.; Corbett, J. T. (Poly-Med, USA). PCT
Int. Pat. WO 9820044; Chem. Abstr. 1998, 129, 19689.
a All reactions run in toluene (1.8 M lactone). b Anhydride yield
determined from the 1H NMR spectrum of reaction mixture; no other
products detected. c Product is (S)-methylsuccinic anhydride, 95% ee (GC).
d Product is (S)-methylsuccinic anhydride, 99% ee (GC). e Starting material
is >99% ee (GC).
(3) For selected uses of succinic anhydrides as paper sizing agents, see:
Sundberg, K.; Roberts, J.; Zetter, C.; Peng, G. (Raisio Chemicals Ltd.,
Finland). PCT Int. Pat. WO 2003106767; Chem. Abstr. 2003, 140, 43662.
(4) In addition to dehydration of the corresponding diacid, or maleic anhydride/
diene Diels-Alder reactions, succinic anhydrides have been made by Pd-
mediated carbonylation of alkynes, alkenes, and alkenoic acids: (a) Heck,
R. F. J. Am. Chem. Soc. 1972, 94, 2712-2716. (b) Chiusoli, G. P.; Costa,
M.; Cucchia, L.; Gabriele, B.; Salerno, G.; Veltri, L. J. Mol. Catal. A
2003, 204, 133-142. (c) Drent, E. (Shell Internationale Research
Maatschappij B. V., Neth.). Eur. Pat. EP 293053; Chem. Abstr. 1989,
110, 212607. (d) Osakada, K.; Doh, M. K.; Ozawa, F.; Yamamoto, A.
Organometallics 1990, 9, 2197-2198.
Lactones with bulkier substituents, such as ethyl and decyl, at
the â-position are also converted to the corresponding anhydrides
(entries 5 and 6). These substrates are generally slower to react
and thus require higher catalyst loadings to reach the desired con-
version in 24 h. Alkyl ether substitution is tolerated (entry 7), as is
bulky, synthetically modifiable substitution such as a tert-butyldim-
ethylsilyl ether (entry 8). Also synthetically useful is olefinic sub-
stitution (entry 9), which is tolerated. When unsubstituted at the
â-position, the substrate is dramatically more reactive. For example,
carbonylation of â-propiolactone reaches high conversion at the
lowest catalyst loading, despite also being run at the lowest tem-
perature (entry 10). This striking increase in reactivity as a function
of decreased steric hindrance is consistent with the proposed
nucleophilic attack on the â-carbon of the lactone (Scheme 1).
The carbonylation of thietanes and oxetanes to produce γ-lactones
using other catalysts has been studied.11b When subjected to
carbonylation in the presence of 2, oxetane (6) is cleanly and
selectively converted to γ-butyrolactone (7) (eq 2).
(5) Another route to succinic anhydrides is the carbonylation of allylic
chlorides catalyzed by Ni(CO)4/MgO: Chiusoli, G. P.; Cometti, G.;
Merzoni, S. Organomet. Chem. Synth. 1972, 1, 439-446.
(6) In related chemistry, metal-bound lactones have been converted to metal
bound anhydrides: (a) Edwards, A. J.; Mays, M. J.; Raithby, P. R.; Solan,
G. A. Organometallics 1996, 15, 4085-4088. (b) Lee, L.; Chen, D. J.;
Lin, Y. C.; Lo, Y. H.; Lin, C. H.; Lee, G. H.; Wang, Y. Organometallics
1997, 16, 4636-4644.
(7) (a) Spivey, A.; Andrews, B. Angew. Chem., Int. Ed. 2001, 40, 3131-
3135. (b) Chen, Y.; McDaid, P.; Deng, L. Chem. ReV. 2003, 103, 2965-
2983.
(8) (a) Getzler, Y. D. Y. L.; Mahadevan, V.; Lobkovsky, E. B.; Coates, G.
W. J. Am. Chem. Soc. 2002, 124, 1174-1175. (b) Mahadevan, V.; Getzler,
Y. D. Y. L.; Coates, G. W. Angew. Chem., Int. Ed. 2002, 41, 2781-
2784. (c) Coates, G. W.; Getzler, Y. D. Y. L.; Wolczanski, P.; Mahadevan,
V. (Cornell Research Foundation, Inc. USA). PCT Int. Pat. WO
2003050154; Chem. Abstr. 2003, 139, 54560. (d) Schmidt, J. A. R.;
Mahadevan, V.; Getzler, Y. D. Y. L.; Coates, G. W. Org. Lett. 2004, 6,
373-376. (e) Getzler, Y. D. Y. L.; Mahadevan, V.; Lobkovsky, E. B.;
Coates, G. W. Pure Appl. Chem. 2004, 76, 557-564.
(9) (a) Drent, E.; Kragtwijk, E. (Shell Internationale Research Maatschappij
B.V., Neth.). Eur. Pat. EP 577206; Chem. Abstr. 1994, 120, 191517. (b)
Lee, J. T.; Thomas, P. J.; Alper, H. J. Org. Chem. 2001, 66, 5424-5426.
(c) Allmendinger, M.; Eberhardt, R.; Luinstra, G. A.; Molnar, F.; Rieger,
B. Z. Anorg. Allg. Chem. 2003, 629, 1347-1352. (d) Molnar, F.; Luinstra,
G. A.; Allmendinger, M.; Rieger, B. Chem.-Eur. J. 2003, 9, 1273-1280.
(10) (a) Alper, H.; Urso, F.; Smith, D. J. H. J. Am. Chem. Soc. 1983, 105,
6737-6738. (b) Alper, H.; Hamel, N. Tetrahedron Lett. 1987, 28, 3237-
3240. (c) Chamchaang, W.; Pinhas, A. R. J. Chem. Soc., Chem. Commun.
1988, 11, 710-711. (d) Chamchaang, W.; Pinhas, A. R. J. Org. Chem.
1990, 55, 2943-2950. (e) Piotti, M. E.; Alper, H. J. Am. Chem. Soc.
1996, 118, 111-116.
In summary, we have discovered that complex 2 is effective for
the selective and efficient carbonylation of â-lactones to produce
succinic anhydrides. As with epoxide carbonylation, we propose
that other complexes of the general form [Lewis acid]+[metal
carbonyl]- have the potential to catalyze this carbonylation. The
reaction rate is strongly dependent on the sterics of substitution at
the â-carbon of the lactone, and the reaction proceeds with clean
inversion of stereochemistry at this site. These data are consistent
with nucleophilic attack by [Co(CO)4]- at the â-carbon of the
lactone. This discovery adds to a portfolio of single carbon
heterocycle expansions, and we anticipate it will find broad utility
in many areas of polymer and organic synthesis.
(11) (a) Brima, T. S. (National Distillers and Chemical Corp., USA). U.S. Pat.
US 4968817; Chem. Abstr. 1991, 114, 185246. (b) Wang, M.; Calet, S.;
Alper, H. J. Org. Chem. 1989, 54, 20-21.
(12) (a) Xu, H.; Jia, L. Org. Lett. 2003, 5, 1575-1577. (b) Khumtaveeporn,
K.; Alper, H. Acc. Chem. Res. 1995, 28, 414-422. (c) Okuro, K.; Dang,
T.; Khumtaveeporn, K.; Alper, H. Tetrahedron Lett. 1996, 37, 2713-
2716. (d) Komatsu, M.; Tamabuchi, S.; Minakata, S.; Ohshiro, Y.
Heterocycles 1999, 50, 67-70.
(13) Mori, Y.; Tsuji, J. Bull. Chem. Soc. Jpn. 1969, 42, 777-779.
(14) Roberto, D.; Alper, H. Organometallics 1984, 3, 1767-1769.
(15) Alper, H.; Arzoumanian, H.; Petrignani, J. F.; Saldana-Maldonado, M. J.
Chem. Soc., Chem. Commun. 1985, 340-341.
(16) O’Brien, E.; Bercot, E.; Rovis, T. J. Am. Chem. Soc. 2003, 125, 10498-
10499.
Acknowledgment. This communication is dedicated to the
memory of Mr. Vinod Kundnani. We thank Dr. Joseph A. R.
Schmidt for generously supplying several â-lactones and Rodney
Bowen of Cornell’s LASSP machine shop for reactor fabrication.
G.W.C. gratefully acknowledges a Packard Foundation Fellowship
(17) For 4, ν(CO) ) 1785 (m), 1835 (w) cm-1; for â-butyrolactone, ν(CO)
)
1835 cm-1
.
(18) Yang, H. W.; Romo, D. Tetrahedron 1999, 55, 6403-6434.
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