The [2+2]-cycloaddition reaction of bisallenes: A dramatic substituent effect

Article abstract of DOI:10.1002/cjoc.201090271

The bisallenes 1 possessing a phenylsulfonyl or n-butyl substituent at the internal position of allene moieties could be smoothly transformed to the bicyclo[5.2.0] or bicyclo[6.2.0] derivatives 2 in moderate to excellent yields with good regioselectivity upon refluxing in toluene. This [2+2]-cycloaddition reaction shows an interesting substituent effect as unveiled by comparing with the results of unsubstituted substrates. However, further attention should be paid to the control of the regioselectivity of the [2+2]-cycloaddition involving different C=C bonds.

Full text of DOI:10.1002/cjoc.201090271

FULL PAPER
The [2＋2]-Cycloaddition Reaction of Bisallenes:
A Dramatic Substituent Effect†
Lu, Pinga(陆平)
Ma, Shengming*,a,b(麻生明)
a State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of
Sciences, 345 Linglin Lu, Shanghai 200032, China
b Shanghai Key Laboratory of Green Chemistry and Chemical Process, Department of Chemistry, East China
Normal University, 3663 North Zhongshan Road, Shanghai 200062, China
The bisallenes 1 possessing a phenylsulfonyl or n-butyl substituent at the internal position of allene moieties
could be smoothly transformed to the bicyclo[5.2.0] or bicyclo[6.2.0] derivatives 2 in moderate to excellent yields
with good regioselectivity upon refluxing in toluene. This [2＋2]-cycloaddition reaction shows an interesting sub-
stituent effect as unveiled by comparing with the results of unsubstituted substrates. However, further attention
should be paid to the control of the regioselectivity of the [2＋2]-cycloaddition involving different C＝C bonds.
Keywords allenes, substituent effects, cycloaddition reaction, cyclobutane, phenylsulfonyl group
Introduction
have some influence on the reaction (Scheme 1).4a-4c As
a part of further study, we envisioned to install a func-
tional group at the internal position of allene moieties to
learn their effect on the [2＋2]-cycloaddition reaction.
Cyclobutanes are found as basic structural elements
in many biologically active natural products.1 Their
syntheses and applications as synthetic intermediates
have flourished in recent years.2 As one of the reliable
preparative methods, the [2＋2] reactions of two allene
moieties have been extensively studied for the construc-
tion of different cyclobutanes with different regioselec-
tivities.3 During our further explorations of the chemis-
try of bisallene,4,5 we have observed the controllable [2
＋2]-reaction of bisallenes, delivering the two different
types of cyclobutane derivatives depending on the re-
gioselectivity (Eq. 1).4e
Results and discussion
This study commenced with bisallene 1a possessing
a phenylsulfonyl group6 at the internal 3-position of one
allene moiety. It is found that the reaction of bisallene
1a, under the catalysis of 2.5 mol% [RhCl(CO)2]2 in
CH3CN under reflux, afforded no major product as
judged from TLC analysis, along with 1a being recov-
ered in 12% yield (Scheme 2). We then turned to ex-
plore other reaction conditions. It is interesting to ob-
serve that the reaction of 1a afforded the bicyclo [5.2.0]
derivative 2a in 89% yield, together with the insepara-
ble regioisomer 2a' (2a∶2a'≥97∶3) when it was sim-
ply heated in toluene under reflux (conditions A). As a
comparison, the [2＋2]-cycloaddition of non-subtituted
bisallene 3 in toluene under reflux for 103 h afforded
the cyclobutane derivative 5a in only 11% yield, with 3
being recovered in 72% yield. Meanwhile the reaction
of bisallene 4 with the n-butyl group installed instead of
the phenylsufonyl group provided the expected bicyclic
product 5b and regioisomer 5b' in a ratio of 88.5∶11.5,
however, the reaction is much slower. These results
obviously indicate that the substituent group (phenylsul-
fonyl or butyl group) here plays an important role in this
[2＋2] cycloaddition reaction.7
On the other hand, we have also disclosed the switch
of the cyclometallation pathway of bisallenes when ter-
minal substituents R1 were installed with a different
catalyst, indicating that the terminal substituent(s) may
*
E-mail: masm@sioc.ac.cn
Received June 20, 2010; revised July 13, 2010; accepted July 22, 2010.
Project supported by the National Natural Science Foundation of China (No. 20732005) and the Major State Basic Research Development Program
(No. 2009CB825300).
† Dedicated to the 60th Anniversary of Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.
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Chin. J. Chem. 2010, 28, 1600— 1606

The [2＋2]-Cycloaddition Reaction of Bisallenes: A Dramatic Substituent Effect
Scheme 1
Scheme 2
The substrate scope of the reaction of 1,5-bisallenes
with a phenylsulfonyl substituent affording bicyclo-
[5.2.0] derivatives was then explored (Scheme 3). The
substrate 1b possessing two methyl substituents at the
terminal position of allene moiety smoothly transformed
to cyclobutane derivative 2b in 90% yield under condi-
tions A. The substrate 1c with an extra methyl group at
the vicinal position of the allene moiety afforded the
bicyclic product 2c in 71% yield. The structure of this
product was unambiguously established by X-ray dif-
fraction studies (Figure 1).8 The N-tethered 1,5-bisal-
lenes 1d and 1e afforded the expected bicyclo[5.2.0]
products 2d and 2e in good yields, together with iso-
meric bicyclo[3.2.0] products 2d' and 2e' as determined
by 1H NMR analysis.
Furthermore, the reactions of 1,6-bisallenes 1f—1h
afforded the corresponding bicyclo[6.2.0] derivatives
2f—2h in moderate to good yields under conditions A
Figure 1 ORTEP representation of 2c.
(Scheme 4). It should be noted that the formation of
8-membered ring is not easy.9,10 Here the structure of 2h
was also unambiguously established by X-ray diffrac-
tion studies (Figure 2).11 Again, the N-tether substrate 1i
with two methyl groups installed at the terminal position
of allene moiety afforded the bicyclic products 2i and
2i' in a combined yield of 76%, with a ratio of 2i/2i'
being ≥92∶8.
Chin. J. Chem. 2010, 28, 1600— 1606
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Lu & Ma
FULL PAPER
Scheme 3
The substrate scope of the cycloaddition of
1,5-bisallene 1
Figure 2 ORTEP representation of 2h.
66% yield (Eq. 2).
This [2＋2]-cycloaddtion reaction may involve bi-
radical intermediates12 (Scheme 5). Simply heating bis-
allene 1 forms a carbon-carbon bond between two cen-
ter carbon atoms affording the biradical intermediate
M1, which would lead to the formation of bicylic prod-
uct 2 via intramolecular radical coupling. The formation
of regioisomer 2' obviously could be attributed to the
formation of intermediate M2.
We further compared these results with the reactions
Conclusion
of 1,6-bisallene without a phenylsulfonyl group. When
non-substituted bisallene 6 was heated in toluene under
reflux for 4.5 d, the bicyclic product 7 was isolated in
only 14% yield and starting material 6 was recovered in
In conclusion, we report here a [2＋2]-cycloaddition
reaction of bisallenes which is mediated by the presence
of substituent(s), affording bicyclo[5.2.0] derivatives or
Scheme 4 The substrate scope of the cycloaddtion of 1,6-bisallene 1
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The [2＋2]-Cycloaddition Reaction of Bisallenes: A Dramatic Substituent Effect
4,4-Bis(methoxycarbonyl)-2-(phenylsulfonyl)-8-di-
Scheme 5
methylbicyclo[5.2.0]nona-1,6-diene (2b)
The reaction of 1b (40 mg, 0.1 mmol) in toluene (2
mL) under reflux afforded 36 mg (90%) of 2b: Liquid;
1H NMR (CDCl3, 300 MHz) δ: 7.93—7.84 (m, 2H),
7.66—7.51 (m, 3H), 5.70 (t, J＝4.7 Hz, 1H), 3.52 (s,
6H), 3.06—3.03 (m, 2H), 2.91—2.87 (m, 2H), 2.79 (d,
J＝4.7 Hz, 2H), 1.17 (s, 6H); 13C NMR (CDCl3, 75.4
MHz) δ: 27.0, 35.4, 35.8, 41.0, 44.6, 52.7, 55.0, 124.4,
127.6, 129.0, 129.1, 133.1, 140.8, 149.2, 149.5, 170.3;
IR (neat) ν: 2953, 2925, 2860, 1736, 1647, 1446, 1416,
1364, 1305, 1246, 1206, 1180, 1157, 1140, 1085, 1＋040
bicyclo[6.2.0] derivatives in moderate to excellent
yields with good regioselectivities. The substituent ef-
fect observed here may further be applied to the synthe-
sis of other bicyclic compounds with a four-membered
ring. Due to the presence of a conjugated 1,3-diene unit,
further elaboration may be conducted to construct more
complicated skeleton. Further studies in this area in-
cluding the real role of the substituent in this type of
reaction and the complete control of the regioselectivity
of the [2＋2]-cycloadditions are being pursued in this
laboratory.
＋
－1
cm ; MS (ESI) m/z: 427.0 (M ＋Na), 421.0 (M ＋
NH4); HRMS calcd for C21H24O6SNa (M ＋ ＋Na)
427.1186, found 427.1196.
4,4-Bis(methoxycarbonyl)-5-methyl-2-(phenylsul-
fonyl)bicyclo[5.2.0]nona-1,6-diene (2c)
Experimental section
4,4-Bis(methoxycarbonyl)-2-(phenylsulfonyl)-bi-
cyclo[5.2.0]nona-1,6-diene (2a)
The reaction of 1c (100.2 mg, 0.26 mmol) in toluene
(5.1 mL) under reflux afforded 71.4 mg (71%) of 2c
together with two unknown spots: Solid; m.p.:
1
139—140 ℃ (petroleum ether/ethyl acetate); H NMR
(CDCl3, 300 MHz) δ: 7.90 (d, J＝7.2 Hz, 2H), 7.66—
7.50 (m, 3H), 5.83 (d, J＝6.3 Hz, 1H), 3.66 (s, 3H),
3.35—2.97 (m, 7H), 2.87—2.57 (m, 3H), 0.92 (d, J＝
6.6 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz) δ: 18.2, 27.4,
29.1, 30.2, 39.0, 52.4, 53.0, 58.8, 127.2, 127.7, 129.1,
133.1, 133.8, 137.0, 140.9, 153.1, 169.1, 170.3; IR (KBr)
ν: 2995, 2956, 2929, 2842, 1763, 1740, 1672, 1644,
1587, 1447, 1436, 1413, 1383, 1373, 1347, 1333, 1302,
1293, 1276, 1239, 1201, 1179, 1160, 1142, 1119, 1086,
1065, 1040, 1000 cm ; MS (ESI) m/z: 413.0 (M ＋Na),
391.0 (M＋＋H). Anal. calcd for C20H22O6S: C 61.52, H
5.68; found C 61.51, H 5.86.
Typical procedure: To a Schlenk tube were added
bisallene 1a (37.6 mg, 0.1 mmol) and toluene (2 mL)
under argon. The resulting mixture was heated under
reflux for 32 h. Then the reaction mixture was cooled to
r.t. and evaporated to afford the residue, which was pu-
rified by flash chromatography (eluent: petroleum ether/
ethyl acetate＝4∶1) on silica gel to afford 33.3 mg
(89%) of pure 2a (the ratio of 2a to 2a' was determined
by 1H NMR analysis of the crude product before separa-
tion): Liquid; 1H NMR (CDCl3, 300 MHz) δ: 7.92—7.85
(m, 2H), 7.66—7.50 (m, 3H), 5.76—5.67 (m, 1H), 3.55 (s,
6H), 3.16—3.04 (m, 4H), 2.85—2.75 (m, 2H),
2.73—2.62 (m, 2H); 13C NMR (CDCl3, 75.4 MHz) δ:
27.5, 29.1, 35.0, 36.1, 52.8, 54.8, 127.52, 127.55,
127.57, 129.0, 133.1, 139.1, 140.9, 152.8, 170.4; IR
(neat) ν: 2954, 2926, 2854, 1736, －1446, 1305, 1253,
＋
－1
N-Tosyl-2-(phenylsulfonyl)-8-dimethyl-4-azabicy-
clo[5.2.0]nona-1,6-diene (2d)
1
1204, 1160, 1141, 1086, 1071 cm ; MS (ESI) m/z:
399.1 (M＋Na＋), 394.1 (M＋NH＋4 ); HRMS calcd for
C19H21O6S (M＋＋H) 377.1053, found 377.1051.
The reaction of 1d (44 mg, 0.1 mmol) in toluene (2
Chin. J. Chem. 2010, 28, 1600— 1606
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Lu & Ma
FULL PAPER
mL) under reflux afforded 37 mg (84%) of pure 2d (the
ratio of 2d to 2d' was determined by H NMR analysis
The reaction of 1f (43.2 mg, 0.08 mmol) in toluene
1
(1.6 mL) under reflux afforded 31.4 mg (73%) of pure
1
of the crude product before separation): Solid; m.p.:
2f (the ratio of 2f to 2f' was determined by H NMR
1
144—145 ℃ (petroleum ether/ethyl acetate); H NMR
analysis of the crude product before separation) (eluent:
1
(CDCl3, 300 MHz) δ: 7.96—7.90 (m, 2H), 7.72—7.57
(m, 3H), 7.34 (d, J＝8.1 Hz, 2H), 7.15 (d, J＝8.1 Hz,
2H), 5.72—5.63 (m, 1H), 4.31—4.25 (m, 2H),
4.20—4.10 (m, 2H), 2.37 (s, 3H), 2.18 (d, J＝2.4 Hz,
2H), 1.32 (s, 6H); 13C NMR (CDCl3, 75.4 MHz) δ: 21.4,
26.5, 42.9, 43.5, 50.0, 50.3, 127.3, 128.2, 129.1, 129.23,
129.24, 130.4, 133.6, 136.95, 137.05, 140.2, 143.2,
160.3; IR (KBr) ν: 1598, 1448, 1436, 1380, 1362, 1339,
petroleum ether/ethyl acetate＝5∶1): Liquid; H NMR
(CDCl3, 300 MHz) δ: 7.76 (d, J＝7.2 Hz, 2H), 7.56 (t,
J＝7.4 Hz, 1H), 7.44 (t, J＝7.8 Hz, 2H), 7.37—7.19 (m,
10H), 5.53—5.45 (m, 1H), 5.20 (d, J＝12.5 Hz, 2H),
5.15 (d, J ＝12.5 Hz, 2H), 3.07—3.94 (m, 4H),
2.60—2.47 (m, 4H), 2.15—2.05 (m, 2H); 13C NMR
(CDCl3, 75.4 MHz) δ: 24.1, 28.3, 30.6, 31.2, 56.5, 67.4,
125.0, 127.5, 128.1, 128.2, 128.4, 129.1, 129.6, 133.1,
135.5, 138.8, 140.9, 157.8, 170.4; IR (neat) ν: 3064,
3033, 2949, 1731, 1632, 1498, 1446, 1375, 1305, 1275,
－1
1331, 1307, 1291, 1186,＋1161, 1126, 1095＋, 1064 cm ;
MS (ESI) m/z: 466.1 (M ＋Na), 444.1 (M ＋H). Anal.
calcd for C23H25NO4S2: C 62.28, H 5.68, N 3.16; found
C 62.20, H 5.69, N 2.98.
－1
1244, 1214, 1171, 1145, 1＋103, 1083, 1060, 102＋7 cm ;
MS (ESI) m/z: 565.1 (M ＋Na), 1107.4 (2M ＋Na);
HRMS calcd for C32H30O6SNa (M＋＋Na) 565.1655,
found 565.1650.
N-Tosyl-2-(phenylsulfonyl)-4-azabicyclo[5.2.0]nona-
1,6-diene (2e)
N-Tosyl-2-(phenylsulfonyl)-4-azabicyclo[6.2.0]deca-
1,7-diene (2g)
The reaction of 1g (85.1 mg, 0.2 mmol) in toluene (4
mL) under reflux afforded 51.5 mg (61%) of pure 2g
(eluent: petroleum ether/ethyl acetate＝4∶1—3∶1)
The reaction of 1e (41.8 mg, 0.1 mmol) in toluene (2
mL) under reflux afforded 32.8 mg (78%) of a mixture
of 2e and 2e' (the ratio of 2e to 2e' was determined to be
1
(the ratio of 2g to 2g' was determined by H NMR
1
90∶10 by H NMR analysis). The pure sample of the
analysis of the crude product before separation): Solid;
1
major isomer 2e could be obtained further from recrys-
tallization: Solid; m.p.: 141—142 ℃; 1H NMR (CDCl3,
300 MHz) δ: 7.96—7.92 (m, 2H), 7.73—7.59 (m, 3H),
7.34 (d, J＝8.1 Hz, 2H), 7.14 (d, J＝8.1 Hz, 2H),
5.60—5.54 (m, 1H), 4.42—4.36 (m, 2H), 4.16—4.08
(m, 2H), 2.80 (t, J＝7.5 Hz, 2H), 2.45—2.34 (m, 5H);
13C NMR (CDCl3, 75.4 MHz) δ: 21.5, 27.2, 28.3, 49.8,
50.1, 127.4, 127.7, 128.5, 129.1, 129.3, 133.7, 136.9,
140.5, 140.6, 143.2, 153.6; IR (KBr) ν: 2946, 1641,
m.p. 127—128 ℃ (petroleum ether/ethyl acetate); H
NMR (CDCl3, 300 MHz) δ: 7.99—7.93 (m, 2H),
7.74—7.58 (m, 3H), 7.31 (d, J＝8.0 Hz, 2H), 7.19 (d,
J＝8.0 Hz, 2H), 5.46 (t, J＝6.9 Hz, 1H), 4.15—4.09 (m,
2H), 3.43 (t, J＝5.9 Hz, 2H), 2.99 (t, J＝7.5 Hz, 2H),
2.52—2.33 (m, 7H); 13C NMR (CDCl3, 75.4 MHz) δ:
21.4, 27.2, 28.6, 30.3, 46.0, 48.5, 124.6, 125.1, 126.9,
127.7, 129.1, 129.5, 133.5, 136.1, 140.3, 141.7, 143.2,
155.1; IR (KBr) ν: 2926, 1637, 1597, 1446, 1336, 1305,
－1
－1
1447, 133＋3, 1153, 1092, 1063 cm ; MS(ESI) m/z:
1252, 1151, 1124, 1084, 1049, 1013 cm ; MS (ESI)
438.0 (M ＋Na), 470.0 (M＋ ＋MeOH＋Na). Anal.
calcd for C21H21NO4S2: C 60.70, H 5.09, N 3.37; found
C 60.33, H 5.05, N 3.18.
m/z: 452.0 (M＋ ＋Na), 484.0 (M＋ ＋MeOH＋Na);
HRMS calcd for C22H23NO4S2Na (M＋＋Na) 452.0961,
found 452.0960.
4,4-Bis(benzyloxycarbonyl)-2-(phenylsulfonyl)bi-
cyclo[6.2.0]deca-1,7-diene (2f)
N-Tosyl-2-(phenylsulfonyl)-5-azabicyclo[6.2.0]deca-
1,7-diene (2h)
The reaction of 1h (43.1 mg, 0.1 mmol) in toluene (2
mL) under reflux afforded 39.7 mg (92%) of 2h: Solid;
1
m.p.: 143—144 ℃ (petroleum ether/ethyl acetate); H
NMR (CDCl3, 300 MHz) δ: 7.90 (d, J＝7.5 Hz, 2H),
7.68—7.52 (m, 5H), 7.29 (d, J ＝ 8.4 Hz, 2H),
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The [2＋2]-Cycloaddition Reaction of Bisallenes: A Dramatic Substituent Effect
4,4-Bis(methoxycarbonyl)-2-(n-butyl)bicyclo[5.2.0]-
nona-1,6-diene (5b)
5.35—5.27 (m, 1H), 3.97—3.90 (m, 2H), 3.38 (t, J＝5.7
Hz, 2H), 2.81 (t, J＝7.5 Hz, 2H), 2.62 (t, J＝5.6 Hz,
2H), 2.54—2.39 (m, 5H); 13C NMR (CDCl3, 75.4 MHz)
δ: 21.5, 28.0, 28.2, 30.1, 45.9, 48.9, 122.4, 126.7, 127.1,
127.6, 129.2, 129.5, 133.3, 136.5, 140.7, 140.8, 143.2,
154.8; IR (KBr) ν: 2927, 2858, 1645, 1596, 1461, 1444,
－1
1429, 1336, 1306, 1161,＋1142, 1120, 1084＋, 1043 cm ;
MS (ESI) m/z: 452.0 (M ＋Na), 484.0 (M ＋MeOH＋
Na). Anal. calcd for C22H23NO4S2: C 61.51, H 5.40, N
3.26; found C 61.18, H 5.51, N 2.95.
N-Tosyl-2-(phenylsulfonyl)-10-dimethyl-5-azabi-
cyclo[6.2.0]deca-1,7-diene (2i)
The reaction of 4 (41.2 mg, 0.14 mmol) in toluene (3
mL) under reflux afforded 24.9 mg (60%) of 5b and 4.1
mg (10%) of recovered 4 (eluent: petroleum ether/ethyl
acetate＝30∶1). The ratio of 5b to 5b' was determined
1
by H NMR analysis of the crude reaction mixture be-
fore separation. 5b: Liquid; 1H NMR (CDCl3, 300 MHz)
δ: 5.25—5.19 (m, 1H), 3.69 (s, 6H), 2.75 (s, 4H), 2.48
(s, 4H), 1.94 (t, J＝7.5 Hz, 2H), 1.46—1.22 (m, 4H),
0.90 (t, J＝7.1 Hz, 3H); 13C NMR (CDCl3, 75.4 MHz) δ:
14.0, 22.6, 25.2, 25.9, 29.5, 33.6, 35.9, 39.6, 52.5, 55.7,
116.1, 131.2, 135.5, 141.2, 172.1; IR (neat) ν: 2955,
2930, 2859, 1737, 1435, 1315, 1243, 1201, 1119, 1084,
1057 cm ; MS (EI) m/z: 292 (M＋, 42.38), 217 (100);
HRMS calcd for C17H24O4 (M ) 292.1675, found
292.1676.
The reaction of 1i (46 mg, 0.1 mmol) in toluene (2
mL) under reflux afforded 35 mg (76%) of 2i and 2i'
(inseparable, the ratio of 2i to 2i' was determined by 1H
NMR analysis): Foam; 2i: 1H NMR (CDCl3, 300 MHz)
δ: 8.01—7.89 (m, 2H), 7.67—7.52 (m, 5H), 7.33—7.24
(m, 2H), 5.50—5.42 (m, 1H), 3.87—3.80 (m, 2H), 3.05
(t, J＝5.7 Hz, 2H), 2.56 (t, J＝6.0 Hz, 2H), 2.46—2.35
(m, 5H), 1.49 (s, 6H); The following data are assigned
to 2i': 1H NMR (CDCl3, 300 MHz) δ: 4.84 (s, 1H), 4.60
(s, 1H); 13C NMR (CDCl3, 75.4 MHz) δ: 21.5, 26.5,
29.2, 43.6, 45.3, 46.3, 48.5, 125.2, 126.3, 127.0, 128.4,
129.1, 129.7, 133.2, 136.2, 138.1, 140.5, 143.3, 162.7;
IR (KBr) ν: 2956, 2924, 2866, 1621, 1598, 1495, 1447,
1378, 1339, 1304, 1250, 1158, 1147, 1125, 1086, 1038,
＋
－1
N-Tosyl-4-azabicyclo[6.2.0]deca-1,7-diene (7)
The reaction of 6 (216.7 mg, 0.75 mmol) in toluene
(6 mL) under reflux afforded 31.4 mg (14%) of 7 and
142.7 mg (66%) of recovered 6 (eluent: petroleum
ether/ethyl acetate ＝40 ∶1). 7: Liquid; 1H NMR
(CDCl3, 300 MHz) δ: 7.68 (d, J＝8.1 Hz, 2H), 7.29 (d,
J＝8.1 Hz, 2H), 5.21—5.13 (m, 1H), 4.99—4.92 (m,
1H), 3.81 (d, J＝3.0 Hz, 2H), 3.34 (t, J＝5.3 Hz, 2H),
2.54—2.37 (m, 9H); 13C NMR (CDCl3, 75.4 MHz) δ:
21.5, 27.6, 28.0, 29.9, 47.3, 48.8, 114.1, 119.3, 127.5,
129.4, 135.3, 138.8, 140.4, 143.1; IR (neat) ν: 3031,
2924, 1597, 1493, 1454, 1423, 1399, 1377, 1336, 1305,
＋
－1
1022 cm ; MS (ESI) m/z: 475.0 (M ＋NH4), 480.0
(M＋＋Na); HRMS calcd for C24H28NO4S2 (M＋＋H)
458.1454, found 458.1455.
4,4-Bis(methoxycarbonyl)bicyclo[5.2.0]nona-1,6-
diene (5a)
－1
1291, 1230, 1159, 1118, 1097, 1049, 1019 cm ; MS
(EI) m/z: 289 (M＋, 5.09), 106 (100); HRMS calcd for
The reaction of 3 (136 mg, 0.58 mmol) in toluene
(11 mL) under reflux afforded 15 mg (11%) of 5a and
94 mg (69%) of recovered 3 (eluent: petroleum
ether/ethyl acetate ＝50 ∶1). 5a: Liquid; 1H NMR
(CDCl3, 300 MHz) δ: 5.36—5.28 (m, 2H), 3.70 (s, 6H),
2.81 (d, J＝3.9 Hz, 4H), 2.55 (s, 4H); 13C NMR (CDCl3,
75.4 MHz) δ: 26.2, 36.2, 52.6, 56.2, 118.4, 141.9, 171－.9;
C16H19NSO2 (M＋) 292.1675, found 292.1676.
References and notes
1
(a) Dembitsky, V. M. J. Nat. Med. 2008, 62, 1.
(b) Ortuno, R. M.; Moglioni, A. G.; Moltrasio, G. Y. Curr.
Org. Chem. 2005, 9, 237.
1
IR (neat) ν: 2970, 1737, 1436, 1365, 1229, 1217 cm ;
(c) Hansen, T. V.; Stenstrom, Y. Organic Synthesis: Theor.
Appl. 2001, 5, 1.
MS (EI) m/z:＋236 (M＋, 3.24), 57 (100); HRMS calcd for
C13H16O4 (M ) 236.1049, found 236.1048.
Chin. J. Chem. 2010, 28, 1600— 1606
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
1605

Lu & Ma
FULL PAPER
(d) Bellus, D.; Ernst, B. Angew. Chem., Int. Ed. Engl. 1988,
27, 797.
(a) Rappoport, Z. J.; Liebman, J. F. The Chemistry of
Cyclobutanes, Wiley, Chichester, 2005.
(b) Namyslo, J. C.; Kaufmann, D. E. Chem. Rev. 2003, 103,
1485.
(c) Lee-Ruff, E.; Mladenova, G. Chem. Rev. 2003, 103,
1449.
0.0990, R indices (all data) R1＝0.0384, wR2＝0.1026, a＝
8.2270(3) Å, b＝8.8719(3) Å, c＝13.4377(5) Å, α＝
82.0240(10)°, β ＝ 81.2390(10)°, γ ＝ 81.5790(10)°, V ＝
952.08(6) Å3, T＝296(2) K, Z＝2. Reflections collected/
unique: 11186/3331 (Rint＝0.0156), number of observations
[＞2σ(I)] 3029; parameters, 244. Supplementary crystallo-
graphic data have been deposited at the Cambridge Crystal-
lographic Data Center: CCDC 777608.
2
3
4
(d) Oppolzer, W. Acc. Chem. Res. 1982, 15, 135.
For reviews on the [2＋2] cycloaddition involving allenes,
see:
9
For reviews on synthesis of cyclooctanoids, see:
(a) Sieburth, S. McN.; Cunard, N. T. Tetrahedron 1996, 52,
6251.
(b) Mehta, G.; Singh, V. Chem. Rev. 1999, 99, 881.
(c) Yet, L. Chem. Rev. 2000, 100, 2963.
(a) Pasto, D. J. Tetrahedron 1984, 40, 2805.
(b) Murakami, M.; Matsuda, T. In Modern Allene Chemistry,
Vol. 2, Eds.: Krause, N.; Hashmi, A. S. K., Wiley-VCH,
Weinheim, 2004, pp. 727—815.
10 (a) Gilbertson, S. R.; DeBoef, B. J. Am. Chem. Soc. 2002,
124, 8784.
(c) Ma, S. Chem. Rev. 2005, 105, 2829.
(b) Evans, P. A.; Robinson, J. E.; Baum, E. W.; Fazal, A. N.
J. Am. Chem. Soc. 2002, 124, 8782.
(c) Wender, P. A.; Ihle, N. C.; Correia, C. R. D. J. Am.
Chem. Soc. 1988, 110, 5904.
(d) Wender, P. A.; Correa, A. G.; Sato, Y.; Sun, R. J. Am.
Chem. Soc. 2000, 122, 7815.
(e) Wender, P. A.; Gamber, G. G.; Hubbard, R. D.; Zhang,
L. J. Am. Chem. Soc. 2002, 124, 2876.
(a) Ma, S.; Lu, P.; Lu, L.; Hou, H.; Wei, J.; He, Q.; Gu, Z.;
Jiang, X.; Jin, X. Angew. Chem., Int. Ed. 2005, 44, 5275.
(b) Lu, P.; Ma, S. Org. Lett. 2007, 9, 5319.
(c) Lu, P.; Ma, S. Org. Lett. 2007, 9, 2095.
(d) Ma, S.; Lu, L. Chem. Asian J. 2007, 2, 199.
(e) Ma, S.; Jiang, X.; Chen, X. Angew. Chem., Int. Ed. 2006,
45, 8009.
5
6
(a) Kim, S. M.; Park, J. H.; Kang, Y. K.; Chung, Y. K.
Angew. Chem., Int. Ed. 2009, 48, 4532.
(b) Inagaki, F.; Narita, S.; Hasegawa, T.; Kitagaki, S.; Mu-
kai, C. Angew. Chem., Int. Ed. 2009, 48, 2007.
For reports on the reactions involving allenes with phenyl-
sulfonyl functionality, see:
(a) Padwa, A.; Murphree, S. S.; Ni, Z.; Watterson, S. H. J.
Org. Chem. 1996, 61, 3829.
(b) Flick, A. C.; Caballero, M. J. A.; Padwa, A. Org. Lett.
2008, 10, 1871.
(f) Miller, S. J.; Kim, S.-H.; Chen, Z.-R.; Grubbs, R. H. J.
Am. Chem. Soc. 1995, 117, 2108.
(g) Snapper, M. L.; Tallarico, J. A.; Randall, M. L. J. Am.
Chem. Soc. 1997, 119, 1478.
11 Crystal data for 2h: C22H23NO4S2, Mr ＝429.53, mono-
clinic, space group P2(1)/c. Final R indices [I＞2σ(I)], R1＝
0.0412, wR2＝0.1157, R indices (all data) R1＝0.0473,
wR2 ＝0.1246, a＝14.8344(5) Å, b＝9.9884(4) Å, c＝
14.1291(5) Å, α＝90.00°, β＝94.5000(10)°, γ＝90.00°, V＝
2087.08(13) Å3, T＝296(2) K, Z＝4. Reflections col-
lected/unique: 23582/3674 (Rint＝0.0187), number of ob-
servations [＞2σ(I)] 3200; parameters, 262. Supplementary
crystallographic data have been deposited at the Cambridge
Crystallographic Data Center: CCDC 777609.
(c) Mukai, C.; Nomura, I.; Yamanishi, K.; Hanaoka, M. Org.
Lett. 2002, 4, 1755.
(d) Mukai, C.; Hara, Y.; Miyashita, Y.; Inagaki, F. J. Org.
Chem. 2007, 72, 4454.
7
8
The Mukai group recently reported some examples of [2＋
2]-reaction of bisallenes with phenylsulfonyl substituent as
side reaction, see ref. 5b.
12 (a) Padwa, A.; Filipkowski, M. A.; Meske, M.; Watterson, S.
H.; Ni, Z. J. Am. Chem. Soc. 1993, 115, 3776.
(b) Padwa, A.; Meske, M.; Murphree, S. S.; Watterson, S.
H.; Ni, Z. J. Am. Chem. Soc. 1995, 117, 7071.
Crystal data for 2c: C20H22O6S, Mr＝390.44, triclinic, space
group P-1. Final R indices [I＞2σ(I)], R1＝0.0350, wR2＝
(E1006202 Lu, Y.; Dong, H.)
1606
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© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 1600— 1606