Decarbonylative cycloaddition of phthalic anhydrides with allenes

Article abstract of DOI:10.1021/ol200044y

The decarbonylative cycloadditions of phthalic anhydrides with allenes were performed by using nickel catalyst. The asymmetric variant of the cycloaddition was also achieved by using chiral phosphine ligands to provide δ-lactones enantioselectively.

Full text of DOI:10.1021/ol200044y

ORGANIC
LETTERS
2011
Vol. 13, No. 6
1374–1377
Decarbonylative Cycloaddition of Phthalic
Anhydrides with Allenes
Yosuke Ochi, Takuya Kurahashi,* and Seijiro Matsubara*
Department of Material Chemistry, Graduate School of Engineering, Kyoto University,
Kyoto 615-8510, Japan
tkuraha@orgrxn.mbox.media.kyoto-u.ac.jp; matsub@orgrxn.mbox.media.kyoto-u.ac.jp
Received January 10, 2011
ABSTRACT
The decarbonylative cycloadditions of phthalic anhydrides with allenes were performed by using nickel catalyst. The asymmetric variant of the
cycloaddition was also achieved by using chiral phosphine ligands to provide δ-lactones enantioselectively.
Transition-metal-catalyzed insertion reactions of an
unsaturated carbon-carbon bond into a carbon-oxygen
bond should be one of the most useful transformations,
since the reaction forms carbon-carbon and carbon-oxy-
gen bonds simultaneously.1,2 Herein, we report our results
of a regioselective decarbonylative cycloaddition of phtha-
lic anhydrides with allenes to provide δ-lactones (Scheme 1).
The reaction represents an unprecedented insertion reaction
of a carbon-carbon double bond into a carbon-oxygen
bond. The strategy is also applicable for cycloaddition of
thiophthalic anhydrides with allenes to give δ-thiolactones,
which also represents the first example of a nickel-catalyzed
insertion reaction of a carbon-carbon double bond into
a carbon-sulfide bond.3-8 Asymmetric variants of both
the cycloadditions were also examined by using chiral
phosphine ligands.9,10
We first examined the ligand effects in the decarbonyla-
tive cycloaddition of phthalic anhydride (1) with allene 2a
using Ni(cod)2 as a Ni(0) precursor. The reaction was
performed in refluxing acetonitrile (MeCN) for 12 h,11
(6) For addition of S-C(O)NR2 bond to alkynes, see: (a) Toyofuku,
M.; Fujiwara, S.; Kuniyasu, H.; Kambe, N. J. Am. Chem. Soc. 2005, 127,
9706. (b) Kuniyasu, H.; Kato, T.; Asano, S.; Ye, J.-H.; Ohmori, T.;
Morita, M.; Hiraike, H.; Fujiwara, S.; Terao, J.; Kurosawa, H.; Kambe,
N. Tetrahedron Lett. 2006, 47, 1141.
(7) For addition of S-CN bond to alkynes, see: Kamiya, I.;
Kawakami, J.; Yano, S.; Nomoto, A.; Ogawa, A. Organometallics
2006, 25, 3562.
(1) Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc. 2008,
130, 17226.
(2) Ooguri, A.; Nakai, K.; Kurahashi, T.; Matsubara, S. J. Am.
Chem. Soc. 2009, 131, 13194.
(8) For addition of S-allyl bond to alkynes, see: Hua, R.; Takeda,
H.; Onozawa, S-y.; Abe, Y.; Tanaka, M. Org. Lett. 2007, 9, 263.
(9) For Ni-catalyzed cycloadditions via elimination of N2, see: (a)
Miura, T.; Yamauchi, M.; Murakami, M. Org. Lett. 2008, 10, 3085. (b)
Yamauchi, M.; Morimoto, M.; Miura, T.; Murakami, M. J. Am. Chem.
Soc. 2010, 132, 54. (c) Miura, T.; Yamauchi, M.; Kosaka, A.;
Murakami, M. Angew. Chem., Int. Ed. 2010, 49, 4955. (d) Miura, T.;
Morimoto, M.; Yamauchi, M.; Murakami, M. J. Org. Chem. 2010, 75,
5359.
(3) For reviews on addition of S-X bond to carbon-carbon un-
saturated bonds, see: (a) Han, L.-B.; Tanaka, M. J. Chem. Soc., Chem.
Commun. 1999, 395. (b) Beletskaya, I.; Moberg, C. Chem. Rev. 1999, 99,
3435. (c) Kuniyasu, H. In Catalytic Heterofunctionalization; Togni, A.,
Gr€utzmacher, H., Eds.; Wiley-VCH: Z€urich, Switzerland, 2001; p 217. (d)
Ogawa, A. J. Organomet. Chem. 2000, 611, 463. (e) Kondo, T.; Mitudo,
T. Chem. Rev. 2000, 100, 3205.
(4) For addition of S-CO2R bond to alkynes, see: Hua, R.; Takeda,
H.; Onozawa, S.; Abe, Y.; Tanaka, M. J. Am. Chem. Soc. 2001, 123,
2899.
(10) For Pd-catalyzed cycloadditions via elimination of CO2, see: (a)
Shintani, R.; Murakami, M.; Hayashi, T. J. Am. Chem. Soc. 2007, 129,
12356. (b) Wang, C.; Tunge, J. A. J. Am. Chem. Soc. 2008, 130, 8118. (c)
Shintani, R.; Park, S.; Shirozu, F.; Murakami, M.; Hayashi, T. J. Am.
Chem. Soc. 2008, 130, 16174. (d) Shintani, R.; Park, S.; Hayashi, T. J.
Am. Chem. Soc. 2007, 129, 14866. (e) Shintani, R.; Tsuji, T.; Park, S.;
Hayashi, T. J. Am. Chem. Soc. 2010, 132, 7508. (f) Shintani, R.;
Murakami, M.; Hayashi, T. Org. Lett. 2009, 11, 457. (g) Shintani, R.;
Hayashi, S.; Murakami, M.; Takeda, M.; Hayashi, T. Org. Lett. 2009,
11, 3754.
(5) For addition of S-C(O)R bond to alkynes, see: (a) Sugoh, K.;
Kuniyasu, H.; Sugae, T.; Ohtaka, A.; Takai, Y.; Tanaka, A.; Machino,
C.; Kambe, N.; Kurosawa, H. J. Am. Chem. Soc. 2001, 123, 5108. (b)
Kuniyasu, H.; Kurosawa, H. Chem.;Eur. J. 2002, 2660. (c) Hirai, T.;
Kuniyasu, H.; Kambe, N. Chem. Lett. 2004, 33, 1148. (d) Hirai, T.;
Kuniyasu, H.; Kambe, N. Tetrahedron. Lett. 2005, 46, 117. (e) Hirai, T.;
Kuniyasu, H.; Terao, J.; Kambe, N. Synlett 2005, 1161. (f) Kuniyasu,
H.; Yamashita, F.; Hirai, T.; Ye, J.-H.; Fujiwara, S.; Kambe, N.
Organometallics 2006, 25, 566. (g) Yamashita, F.; Kuniyasu, H.; Terao,
J.; Kambe, N. Org. Lett. 2008, 10, 101.
(11) The reaction did not proceed in a sealed vessel. Refluxing of
reaction solvent is probably essential to promote the exhaust of CO from
the reaction system efficiently.
r
10.1021/ol200044y
Published on Web 02/18/2011
2011 American Chemical Society

Scheme 1. Nickel-Catalyzed Decarbonylative Cycloaddition of
a Phthalic Anhydride with an Allene
Scheme 2. Scope of the Nickel-Catalyzed Decarbonylative
Cycloadditions of Phthalic Anhydride 1 with Allenes 2
Table 1. Optimization of Reaction Conditions for the
Nickel-Catalyzed Decarbonylative Cycloaddition of a Phthalic
Anhydride 1 with an Allene 2aa
These results prompted us to investigate an asymmetric
decarbonylative cycloaddition of phthalic anhydride 1
with alkene 2a by using a chiral ligand in place of PMe2Ph
(Table 2). The reactions with chiral bidentate phosphine
ligands, such as (S,S)-chiraphos12 or (R,R)-Me-duphos,13
gave small amounts of cycloadduct 3a but without enan-
tioselectivity (entries 1-2). Optically active 3a was ob-
tained in 55% yield when (R)-binap was used as a ligand.14
The reaction with (R)-quinap did not afford any cycload-
duct at all,15 while bidentate P-N ligands, such as (S)-iPr-
fox16 or (S,S)-iPr-foxap,17 gave improved results in terms
of both yield and selectivity (entries 5 and 8). The yield and
the enantioselectivity were influenced by the reaction
medium employed. The highest yield and enantioselectiv-
ity were observed when pyridine was used as the reaction
solvent, and 3a was obtained in 73% yield with 59% ee
(entry12). With a shorter reaction time (4 h), 3a was
obtained in 56% yield with 58% ee. Phthalic anhydride 1
alsoreacted with2btoprovide3bin 64% yield with81% ee
(entry 14).
In addition to phthalic anhydride, thiophthalic anhy-
dride 4 also participated in the reaction with allenes 2
(Scheme 3). Cycloaddition of thiophthalic anhydride 4
with 1.5 equiv of allene 2a in the presence of Ni/PMe2Ph
catalysis provided δ-thiolactone 5a in 93% isolated yield.
The use of a different ligand, such as PMe3, PPh3, or PCy3,
in toluene gave inferior results. The reaction of cyclohexyl-
substituted allene 2b with 4 gave the correspondingly
substituted cycloadduct 5b in 87% yield with a regioselec-
tivity of 10/1. Phenyl-substitutedallene2calsoparticipated
in the reaction to give 5c in 87% yield with a 5/1 ratio of
regisoisomers. gem-Dimethyl-substituted allene 2d reacted
entry
ligand (mol %)
2a (equiv)
solvent
yield (%)b
1
PMe3 (40)
1
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
dioxane
pyridine
toluene
43
52
46
<1
<1
<1
64
52
52
61
59
53
2
PMe2Ph (40)
PMePh2 (40)
PPh3 (40)
1
3
1
4
1
5
PCy3 (20)
1
6
bpy (20)
1
7
PMe2Ph (40)
PMe2Ph (40)
PMe2Ph (40)
PMe2Ph (40)
PMe2Ph (40)
PMe2Ph (40)
1.5
3
8
9
1
10
11
12
1.5
1.5
1.5
a Reactions were carried out using Ni(cod)2 (10 mol %), ligand, 1 (0.5
mmol), and 2 in 1 mL of refluxing solvent for 12 h. b Isolated yields.
and the results are summarized in Table 1. Among the
ligands examined, PMe2Ph gave the best result to afford
δ-lactone 3a in 52% yield regioselectively (entry 2). Trace
or lower amounts of 3a were obtained in the cases of using
PPh3, PCy3, and bpy in place of PMe2Ph (entries 4-9). It
was found that the reaction of 1 with 1.5 equiv of 2a gave
the highest yield of 3a in 64% yield (entry 7). In other
solvents such as 1,4-dioxane, pyridine, and toluene, yields
were even lower (entries 10-12). On addition of ZnCl2
(20 mol %), the cycloaddition was retarded.1
We next investigated the scope of the reaction using
various allenes, and the results are summarized in Scheme
2. The reaction of cyclohexyl-substituted allene 2b with
1 afforded 3b in 45% yield, while phenyl-substituted allene
2c failed to participate in the reaction and recovered
unchanged. This feature may suggest that an electron-rich
double bond contributes significantly toward the reactivity
on the cycloaddition. Indeed, the reaction of gem-dimethyl-
substituted allene 2d reacted with 1 to provide a single
product 3d via regioselective insertion of the internal
carbon-carbon double bond of 2d. The cycloaddition of
a cyclic allene 2e gave3e in excellent yield, while the reaction
of 1,3-dipropyl-substituted allene 2f gave cycloadduct 3f as
a 1/1 mixture of regioisomers in 83% yield.
(12) Fryzuk, M. D.; Bosnich, B. J. Am. Chem. Soc. 1977, 99, 6262.
(13) Burk, M. J. J. Am. Chem. Soc. 1991, 113, 8518.
(14) Noyori, R.; Takaya, H. Acc. Chem. Res. 1990, 23, 345.
(15) Alcock, N. W.; Brown, J. M.; Hulmes, D. I. Tetrahedron:
Asymmetry 1993, 4, 743.
(16) (a) Loiseleur, O.; Meier, P.; Pfaltz, A. Angew. Chem., Int. Ed.
Engl. 1996, 35, 200. (b) Lightfoot, A.; Schnider, P.; Pfaltz, A. Angew.
Chem., Int. Ed. 1998, 37, 2897.
(17) Miyake, Y.; Nishibayashi, Y.; Uemura, S. Synlett 2008, 1747.
Org. Lett., Vol. 13, No. 6, 2011
1375

Table 2. Nickel-Catalyzed Asymmetric Decarbonylative Cy-
cloaddition of Phthalic Anhydrides 1 with Allenes 2a
Scheme 3. Scope of the Nickel-Catalyzed Decarbonylative Cy-
cloaddition of Thiophthalic Anhydride 4 with Allenes 2
entry
R
chiral ligand
solvent yield (%)b ee (%)
1
2
3
4
5
6
7
8
9
C5H11 (2a) (S,S)-chiraphos MeCN
C5H11 (2a) (R,R)-Me-duphos MeCN
7
<1
<1
7
Scheme 4. Nickel-Catalyzed Asymmetric Decarbonylative Cy-
cloaddition of Thiophthalic Anhydride 4 with Allene 2
5
C5H11 (2a) (R)-binap
MeCN
MeCN
MeCN
MeCN
MeCN
55
<1
77
67
70
70
37
70
48
73
56c
64
C5H11 (2a) (R)-quinap
C5H11 (2a) (S)-iPr-fox
C5H11 (2a) (S,S)-Bn-foxap
C5H11 (2a) (S,S)-Ph-foxap
-
30
<1
3
C5H11 (2a) (S,S)-iPr-foxap MeCN
C5H11 (2a) (S,S)-tBu-foxap MeCN
39
20
<1
<1
59
58
81
10 C5H11 (2a) (S,S)-iPr-foxap toluene
11 C5H11 (2a) (S,S)-iPr-foxap 1,4-dioxane
12 C5H11 (2a) (S,S)-iPr-foxap pyridine
13 C5H11 (2a) (S,S)-iPr-foxap pyridine
14 Cy (2b)
(S,S)-iPr-foxap pyridine
a Reactions were carried out using Ni(cod)2 (10 mol %), ligand, 1
(0.5 mmol), and 2 in 1 mL of refluxing solvent for 12 h . b Isolated yields.
c Reaction time: 4 h.
with 4 to furnish a single product 5d. The reaction was also
compatible with a cyclic allene 2e to give 5e in 78% yield.
The cycloaddition was also extended to asymmetric
reactions. The reaction of 4 with 2a affords 5a in 99%
yield with 82% ee when (S,S)-iPr-foxap was employed as a
chiral phosphine ligand (Scheme 4). Only minor solvent
effects on enantioselectivity and yield were observed.
Under the same reaction conditions, monosubstituted
allene such as 2b and 2c reacted with 4 to afford the
correspondingly substituted optically active cycloadducts
5b and 5c in excellent yields.
phthalimide 6 with allene 2a for 12 h afforded cycloadduct
7a in 48% yield with 82% ee. Monosubstituted allene 2b
also reacted with 6 to afford the correspondingly substi-
tuted optically active cycloadducts 7b and in 40% yield
(82% ee), while phenyl-substituted allene 2c did not parti-
cipate in the reaction.
A plausible reaction pathway to account for the forma-
tion of cycloadducts 3, 5, and 7 based on the observed
results is outlined in Scheme 6. The catalytic cycle of the
Furthermore, the enantio- and regioselective cycloaddi-
tion of phthalimide with allene was briefly examined
(Scheme 5).18,19 The reaction of N-pyrrol-substituted
(20) (a) O’Brien, E. M.; Bercot, E. A.; Rovis, T. J. Am. Chem. Soc.
2003, 125, 10498. (b) Johnson, J. B.; Bercot, E. A.; Rowley, J. M.;
Coates, G. W.; Rovis, T. J. Am. Chem. Soc. 2007, 129, 2718.
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2009, 131, 7494. (b) Yoshino, Y.; Kurahashi, T.; Matsubara, S. Chem.
Lett. 2010, 39, 896.
(18) (a) Kajita, Y.; Kurahashi, T.; Matsubara, S. J. Am. Chem. Soc.
2008, 130, 6058. (b) Fujiwara, K.; Kurahashi, T.; Matsubara, S. Org.
Lett. 2010, 12, 4548.
(19) For oxidative addition of C-N bond to Ni, see: (a) Chan, Y. W.;
Renner, M. W.; Balch, A. L. Organometallics 1983, 2, 1888. (b) Lin,
B. L.; Clough, C. R.; Hillhouse, G. L. J. Am. Chem. Soc. 2002, 124, 2890.
(c) Ozerov, O. V.; Guo, C.; Fan, L.; Foxman, B. M. Organometallics
2004, 23, 5573.
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Sano, K.; Yamamoto, T.; Yamamoto, A. Chem. Lett. 1984, 941. (c)
Sano, K.; Yamamoto, T.; Yamamoto, A. Bull. Chem. Soc. Jpn. 1984, 57,
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€
Schonecker, B. J. Organomet. Chem. 1993, 447, 131.
1376
Org. Lett., Vol. 13, No. 6, 2011

Scheme 5. Nickel-Catalyzed Asymmetric Decarbonylative Cy-
cloaddition of Phthalimide 6 with Allenes 2
Scheme 6. Plausible Reaction Pathway for the Nickel-Catalyzed
Decarbonylative Cycloadditions
present reactions may consist of oxidative addition of a
CO-X bond to a Ni(0) complex.1,5,19-22 Subsequent
decarbonylation and coordination of allene 2 take place
to give nickel(II) intermediate 10. The allene would then
insertinto the C-Ni bond togivethe morestable acyclic π-
allylnickel intermediate 11.23,24 Nucleophilic addition of a
heteroatom onto π-allylnickel at the more substituted
carbon takes place to afford cycloadducts and regenerate
the starting Ni(0) complex.
In summary, we have developed a decarbonylative
cycloaddition of phthalic anhydride with allene to give
δ-lactone in a single step. The reaction represents an
unprecedented insertion reaction of a carbon-carbon
double bond into a carbon-oxygen bond. We also de-
monstrated for the first time that δ-thiolactone can be
prepared via decarbonylative cycloaddition of thiophtha-
lic anhydride with allene.25 Moreover, asymmetric inser-
tion reactions of a carbon-carbon double bond into a
carbon-oxygen bond and into a carbon-sulfide bond
were also successfully demonstrated with chiral phosphine
ligands to provide δ-lactones and δ-thiolactones.
(23) For migratory insertion of allenes into oxanickelacycles, see:
€
Hoberg, H.; Peres, Y.; Kruger, C.; Tsay, Y.-H. Angew. Chem., Int. Ed.
1987, 26, 771.
Acknowledgment. This work was supported by Grants-
in-Aid from the Ministry of Education, Culture, Sports,
Science, and Technology, Japan. T.K. also acknowledges
the Novartis Foundation, Asahi Glass Foundation,
Kansai Research Foundation, and Mizuho Foundation
for the Promotion of Sciences.
(24) It was found that racemic cycloadduct 3a was recovered un-
changed when it was subjected to the Ni/(S,S)-iPr-foxap catalyst (1).
This result may indicate that a reductive elimination step is an irrever-
sible process. Meanwhile, the reaction of phthalic anhydride 1 with
chiral allene 2f (95% ee) in the presence of the Ni/PMe2Ph catalyst gave
racemic cycloadducts 3f (2). This may clearly suggest that the reaction
proceeds via π-allylnickel 11, which is a key intermediate for chiral
induction.
Supporting Information Available. Experimental pro-
cedures including spectroscopic and analytical data of
new compounds. This material is available free of charge
via the Internet at http://pubs.acs.org.
(25) Functionalized δ-lactones are ubiquitous in a variety of biolo-
gically active natural products. For recent examples, see: (a) Munro,
T. A.; Rizzacasa, M. A.; Roth, B. L.; Toth, B. A.; Yan, F. J. Med. Chem.
2005, 48, 345. (b) Nicotra, V. E.; Gil, R. R.; Oberti, J. C.; Burton, G. J.
Nat. Prod. 2007, 70, 808. (c) Thompson, C. M.; Quinn, C. A.; Hergen-
rothe, P. J. J. Med. Chem. 2009, 52, 117. (d) Meragelman, T. L.;
Scudiero, D. A.; Davis, R. E.; Staudt, L. M.; McCloud, T. G.; Cardelli-
na, J. H., II; Shoemaker, R. H. J. Nat. Prod. 2009, 72, 336. (e) Haritakun,
R.; Sappan, M.; Suvannakad, R.; Tasanathai, K.; Isaka, M. J. Nat.
Prod. 2010, 73, 75.
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