Sulfur ylides 13. Synthesis and intramolecular cyclization of keto-stabilized sulfur ylides

Article abstract of DOI:10.1007/s11172-006-0202-6

Keto-stabilized sulfur mono-and bisylides were obtained from N-phthalylglutamic acid and their intramolecular cyclization was studied. The intramolecular cyclization of the ylide obtained at the α-carboxy group gave a product of the pyrrolizidinedione structure; bisylide yielded a cycloheptene derivative as the result of intramolecular recombination of intermediate dicarbene. The ylide obtained at the γ-carboxy group underwent no cyclization, giving methylthio ketone and oxo benzoate.

Full text of DOI:10.1007/s11172-006-0202-6

Russian Chemical Bulletin, International Edition, Vol. 54, No. 12, pp. 2867—2872, December, 2005
2867
Sulfur ylides
13.* Synthesis and intramolecular cyclization of
ketoꢀstabilized sulfur ylides
F. Z. Galin, I. M. Sakhautdinov, S. N. Lakeev, V. A. Egorov, A. A. Fatykhov, and I. O. Maidanovaꢀ
Institute of Organic Chemistry, Ufa Research Center of the Russian Academy of Sciences,
71 prosp. Oktyabrya, 450054 Ufa, Russian Federation.
Fax: +7 (347 2) 35 6066, 35 2641. Eꢀmail: galin@anrb.ru, irina_m@anrb.ru
Ketoꢀstabilized sulfur monoꢀ and bisylides were obtained from Nꢀphthalylglutamic acid
and their intramolecular cyclization was studied. The intramolecular cyclization of the ylide
obtained at the αꢀcarboxy group gave a product of the pyrrolizidinedione structure; bisylide
yielded a cycloheptene derivative as the result of intramolecular recombination of intermediate
dicarbene. The ylide obtained at the γꢀcarboxy group underwent no cyclization, giving
methylthio ketone and oxo benzoate.
Key words: Nꢀphthalylglutamic acid, ketoꢀstabilized sulfonium ylide, intramolecular cyꢀ
clization, intramolecular recombination of dicarbene.
To proceed further in our investigations concerning
the synthesis of ketoꢀstabilized sulfonium ylides from
αꢀ and βꢀamino acids and their intramolecular cyclizaꢀ
tion,1—8 we obtained novel sulfur ylides from Nꢀphthalylꢀ
glutamic acid. Dibasic glutamic acid can form three sulꢀ
fur ylides involving either the αꢀ or γꢀcarboxyl groups or
both (they are conventionally denoted as αꢀylide, γꢀylide,
and bisylide, respectively).
The structures of diazo ketones 3, 10, and 16 were
confirmed by spectroscopic data. Their IR spectra conꢀ
tain intense absorption bands of the diazo group at ν =
2116 (3) and 2110 cm–1 (10, 16). In the 13C NMR specꢀ
tra, signals for the C atoms of the CHN2 group appear at
δC 54.75 (3), 54.94, 54.3 (10), and 54.6 (16). The 1H NMR
spectra show a singlet for the CHN2 proton at δH 5.22 (3),
5.22, 5.48 (10), and 5.48 (16).
As shown earlier,5,8 sulfonium ylides can be obtained
from amino acids in two ways: by the salt method
(deprotonation of a sulfonium salt prepared from the corꢀ
responding diazo ketone8) or by the carbene method (reꢀ
action of Me2S with a carbene generated from diazo keꢀ
tone in the presence of a catalyst5). In the latter case, the
ylide is involved in in situ intramolecular cyclization. To
compare both the methods in efficiency, we synthesized
ylides in either way.
In Schemes 1—3, the syntheses of γꢀylide 6, bisylide 13,
and αꢀylide 19 are shown, respectively.
γꢀYlide 6 was obtained from diazo ketone 3 prepared
by the Arndt—Eistert reaction of Nꢀphthalylglutamic acid
(1) with SOCl2 to predominantly form anhydride 2, which
was then treated with a solution of diazomethane in
CH2Cl2.
Subsequently, ylides 6, 13, and 19 were synthesized
according to a general procedure.
In the case of the salt method, diazo ketones 3, 10,
and 16 were treated with aqueous HBr to give αꢀbromoꢀ
methyl ketones 4, 11, and 17, whose reactions with Me2S
yielded sulfonium salts 5, 12, and 18. Their deprotonation
with NaH in THF under argon gave ketoꢀstabilized sulfur
ylides 6, 13, and 19, respectively.
The structures of all the compounds obtained were
confirmed by spectroscopic data. In the 13C NMR spectra
of bromo ketones 4, 11, and 17, signals for the methylene
C atom of the CH2Br group at δC 36.07 (4), 30.56,
36.45 (11), and 30.93 (17) are informative. The 1H NMR
spectra of sulfonium salts 5, 12, and 18 show singlets for
the methyl protons of the SMe2 group at δH 2.8.
It is worth noting that all the ylides obtained are unꢀ
stable and rapidly decompose into several products even
at room temperature, which makes it difficult to record
the spectra of individual ylides. Yet they can be detected
from a longerꢀwavelength shift (characteristic of ketoꢀ
stabilized ylides) of the absorption band of the CO group
bound to the carbanion to ν = 1540 cm–1 in the IR specꢀ
tra and from an upfield shift of the signal for the C atom of
this group to δ 182 in the 13C NMR spectra, which sugꢀ
For the synthesis of bisylide 13, Nꢀphthalylglutamic
acid 1 was converted into dichloride 9 with PCl5 and then
into bis(diazo ketone) 10 in 98% yield.
For the synthesis of αꢀylide 19, αꢀdiazo ketone 16 was
obtained from γꢀmethyl Nꢀphthalylglutamate 15 by the
Arndt—Eistert reaction.
* For Part 12, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2771—2776, December, 2005.
1066ꢀ5285/05/5412ꢀ2867 © 2005 Springer Science+Business Media, Inc.

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Galin et al.
Scheme 1
Reagents and conditions: a. SOCl2, PhH, 80 °C; b. CH2N2, CH2Cl2, –5 °C; c. HBr, CH2Cl2, ~20 °C; d. Me2S, Me2CO, ~20 °C;
e. NaH, THF, ~20 °C; f. Rh2(OAc)4, Me2S, PhH, 80 °C; g. BzOH, PhMe, 110 °C.
gests delocalization of the negative charge on the carboꢀ
nyl group. The formation of ylides was also confirmed
by elemental analysis data immediately upon their synꢀ
theses.
sence of benzoic acid, the reaction gives sulfide 7 in
35% yield (with respect to diazo ketone).
Under the conditions of intramolecular cyclization,
bisylide 13 converted into cycloheptene derivative 14,
which can be explained by the generation of an intermeꢀ
diate dicarbene from bisylide 13.9 The yield of product 14
was 40% (with respect to ylide 13) or 12% (with respect to
diazo ketone 10) for the salt method and 17% for the
carbene method.
αꢀYlide 19 underwent spontaneous cyclization even
at room temperature to give pyrrolizidinedione 20. In
boiling toluene in the presence of BzOH, its yield was
56% (with respect to ylide 19) or 31% (with respect to
diazo ketone 16). Under the same conditions, ylide 19
obtained according to the carbene method underwent
intramolecular cyclization to give product 20 in 10% yield.
Thus, we obtained novel ketoꢀstabilized sulfonium
ylides from Nꢀphthalylglutamic acid. It was found that
only αꢀylide 19 undergoes intramolecular cyclization into
a pyrrolizidinedione structure, while for ylides 6 and 13,
In the case of the carbene method, ylide were obꢀ
tained by decomposition of diazo ketones 3, 10, and 16 in
the presence of Me2S and the catalyst Rh2(OAc)4 in boilꢀ
ing benzene. Benzene was used as a solvent because of the
high stabilities of diazo ketones, which keep inert at lower
temperatures. The course of the reactions and the formaꢀ
tion of ylides was monitored by TLC. After removal of the
solvent and addition of toluene and BzOH, we attempted
intramolecular cyclization of ylides 6, 13, and 19.
The study of the behavior of the ylides under the conꢀ
ditions of intramolecular cyclization (boiling toluene, an
equimolar amount of BzOH as a catalyst)7 revealed that
sulfur γꢀylide 6 yields acyclic sulfide 7 (19%) and oxo
benzoate 8 (32%). Ylide 6 obtained according to the
carbene method under the same conditions forms a diffiꢀ
cultꢀtoꢀseparate mixture of products. However, in the abꢀ

Sulfur ylides from Nꢀphthalylglutamic acid
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 12, December, 2005 2869
Scheme 2
Reagents and conditions: a. PCl5, CCl4, 77 °C; b. CH2N2, CH2Cl2, –5 °C; c. HBr, CH2Cl2, ~20 °C; d. Me2S, Me2CO, ~20 °C;
e. NaH, THF, ~20 °C; f. Rh2(OAc)4, Me2S, PhH, 80 °C; g. BzOH, PhMe, 110 °C.
Scheme 3
Reagents and conditions: a. SOCl2, PhH, 80 °C; b. CH2N2, CH2Cl2, –5 °C; c. HBr, CH2Cl2, ~20 °C; d. Me2S, Me2CO, ~20 °C;
e. NaH, THF, ~20 °C; f. Rh2(OAc)4, Me2S, PhH, 80 °C; g. BzOH, PhMe, 110 °C.
competitive reactions are thermodynamically more faꢀ
vorable: generation of an intermediate dicarbene followed
by its intramolecular recombination for ylide 13 and the
formation of methylthio ketone and oxo benzoate for
ylide 6. The relatively low yields of the compounds obꢀ
tained are due to the instabilities of ylides, which decomꢀ

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Galin et al.
The precipitate of anhydride 2 (18%) that formed was filtered
off. The solvent was removed to give acid dichloride 9 in 79%
yield, which was employed without additional purification for
the synthesis of bis(diazo ketone) 10 as described above. A soluꢀ
tion of acid dichloride 9 (3 g, 10 mmol) in CH2Cl2 (20 mL)
and a solution of diazomethane prepared from NMU (6.6 g,
80 mmol) were used.
The yield of compound 10 was 98%. Found (%): C, 55.31;
H, 3.10; N, 21.87. C15H11N5O4. Calculated (%): C, 55.39;
H, 3.41; N, 21.53. IR, ν/cm–1: 1636, 1714, 1774, 2110. 1H NMR,
δ: 2.34—2.40, 2.50—2.58 (both m, 2 H each, CH2); 4.79—4.85
(m, 1 H, CH); 5.22, 5.48 (both s, 1 H each, CH); 7.69—7.90 (m,
4 H, C6H4). 13C NMR, δ: 23.4, 37.0, 54.3, 54.9, 56.5, 123.7,
131.5, 134.5, 167.8, 189.1, 192.9.
pose under the reaction conditions to give many byꢀprodꢀ
ucts that are difficult to separate.
Experimental
IR spectra were recorded on a URꢀ20 and Specord Mꢀ80
instruments (Nujol). 1H and 13C NMR spectra were recorded
on a Bruker AMꢀ300 spectrometer (300 and 75 MHz, respecꢀ
tively) in CDCl3 (except for salts 5, 12, and 18) with Me4Si as
the internal standard. The course of the reactions was monitored
by TLC on Silufol UVꢀ254 plates; spots were visualized under
UV light, in the iodine vapor, and with ninhydrin or with a
solution of anisaldehyde followed by heating to 100—120 °C.
Reaction products were isolated by column chromatography on
silica gel with light petroleum—ethyl acetate (8 : 2) as an eluent.
The solvents Me2CO and CCl4 were distilled over P2O5, toluene
and benzene were refluxed and distilled over metallic sodium,
SOCl2 and CH2Cl2 were distilled, and Me2S was dried over 4A
molecular sieves. Phthalic anhydride (analytical grade), glutamic
acid (highꢀpurity grade), methyl glutamate (highꢀpurity grade),
PCl5 (analytical grade), 48% HBr (analytical grade), NaH
(60—65% dispersion in an oil; Fluka) were used as purchased.
2ꢀ(1,3ꢀDioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)pentanedioic
acid (1) and 2ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀ
methoxyꢀ5ꢀoxopentanoic acid (15) were prepared according to a
known procedure.10
Methyl 6ꢀdiazoꢀ2ꢀ(1,3ꢀdioxoꢀ1,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ
5ꢀoxohexanoate (3) and methyl 6ꢀdiazoꢀ4ꢀ(1,3ꢀdioxoꢀ2,3ꢀdiꢀ
hydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀoxohexanoate (16). Thionyl chloride
(50 mmol) was added to a suspension of compound 1 or 15
(20 mmol) in dry benzene (100 mL) and the reaction mixture
was refluxed until gas evolution ceased (~3 h). The solvent and
the excess of SOCl2 were removed and the resulting acid chloꢀ
ride was used without additional purification in a reaction with
CH2N2. A solution of the acid chloride (10 mmol) in CH2Cl2
(20 mL) was added dropwise at –5 °C to a stirred solution of
CH2N2 in CH2Cl2 prepared from nitrosomethylurea (NMU)
(40 mmol). The solution was stirred at this temperature for 0.5 h
and left in a refrigerator for 12 h. The solvent was removed and
diazo ketones 3 and 16 were isolated by column chromatoꢀ
graphy.
2ꢀ(2,6ꢀDioxotetrahydroꢀ2Hꢀpyranꢀ3ꢀyl)ꢀ1Hꢀisoindoleꢀ
1,3(2H )ꢀdione (2). The yield was 18%. Found (%): C, 60.29;
H, 2.9; N, 5.3. C13H9NO5. Calculated (%): C, 60.24; H, 3.5;
N, 5.4. IR, ν/cm–1: 1646, 1724, 1764.
2ꢀ(1,3ꢀDioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)pentanedioyl
dichloride (9). The yield was 79%. Found (%): C, 49.32; H, 3.24;
Cl, 22.56; N, 4.53. C13H9Cl2NO4. Calculated (%): C, 49.71;
H, 2.89; Cl, 22.57; N, 4.46. IR, ν/cm–1: 1646, 1795, 1798.
Synthesis of bromo ketones (general procedure). A 48% aqueꢀ
ous solution of HBr (1 mL) was added to a stirred solution of
diazo ketone (1 mmol) in CH2Cl2 (10 mL). After gas evoluꢀ
tion ceased, the solution was stirred for 1 h and the organic
layer was separated, washed with 5% Na2CO3, and dried over
MgSO4. The solvent was removed and the residue was chromatoꢀ
graphed.
Methyl 6ꢀbromoꢀ2ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀ
yl)ꢀ5ꢀoxohexanoate (4). The yield was 82%. Found (%): C, 49.01;
H, 3.63; Br, 22.1; N, 4.23. C15H14BrNO5. Calculated (%):
C, 48.93; H, 3.83; Br, 21.7; N, 3.8. IR, ν/cm–1: 1636, 1714,
1774, 1750. 1H NMR, δ: 2.31—2.69, 2.71—2.79 (both m,
2 H each, CH2); 3.69 (s, 3 H, Me); 3.85 (s, 2 H, BrCH2);
4.79—4.88 (m, 1 H, CH); 7.69—7.88 (m, 4 H, C6H4). 13C NMR,
δ: 23.1, 33.9, 36.0, 50.7, 52.7, 123.7, 131.4, 134.3, 167.3,
169.0, 200.5.
2ꢀ(1,7ꢀDibromoꢀ2,6ꢀdioxoheptanꢀ3ꢀyl)ꢀ1Hꢀisoindoleꢀ
1,3(2H )ꢀdione (11). The yield was 93%. Found (%): C, 41.6;
H, 3.12; Br, 36.95; N, 3.2. C15H14BrNO5. Calculated (%):
C, 41.79; H, 3.04; Br, 37.07; N, 3.25. IR, ν/cm–1: 1636,
1
The yield of compound 3 was 71%. Found (%): C, 57.03;
H, 4.17; N, 13.25. C15H13N3O5. Calculated (%): C, 57.14;
H, 4.16; N, 13.33. IR, ν/cm–1: 1636, 1714, 1774, 1750, 2116.
1H NMR, δ: 2.32—2.52, 2.52—2.69 (both m, 2 H each, CH2);
3.71 (s, 3 H, Me); 4.85—4.93 (m, 1 H, CH); 5.22 (s, 1 H, CH);
7.69—7.90 (m, 4 H, C6H4). 13C NMR, δ: 24.2, 30.5, 51.7, 52.8,
54.7, 123.6, 131.6, 134.3, 167.5, 169.2, 192.9.
The yield of compound 16 was 62%. Found (%): C, 56.8;
H, 4.45; N, 13.64. C15H13N3O5. Calculated (%): C, 57.14;
H, 4.16; N, 13.33. IR, ν/cm–1: 1650, 1731, 1780, 2110. 1H NMR,
δ: 2.29—2.37, 2.44—2.54 (both m, 2 H each, CH2); 3.55 (s, 3 H,
Me); 4.78—4.87 (m, 1 H, CH); 5.48 (s, 1 H, CH); 7.69—7.88
(m, 4 H, C6H4). 13C NMR, δ: 23.2, 30.4, 51.6, 54.6, 56.0, 123.5,
131.3, 134.3, 167.5, 172.5, 188.9.
1714, 1774, 1750. H NMR, δ: 2.42—2.78, 2.60—2.68 (both m,
2 H each, CH2); 4.12, 3.85 (both s, 2 H each, BrCH2);
5.09—5.24 (m, 1 H, CH); 7.71—7.88 (m, 4 H, C6H4).
13C NMR, δ: 23.1, 34.0, 35.9, 50.7, 52.7, 123.7, 131.4, 134.3,
167.3, 169.0, 200.5.
Methyl 6ꢀbromoꢀ4ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀ
yl)ꢀ5ꢀoxohexanoate (17). The yield was 99%. Found (%): C, 49.1;
H, 3.54; Br, 21.5; N, 4.59. C15H14BrNO5. Calculated (%):
C, 48.93; H, 3.83; Br, 21.7; N, 3.8. IR, ν/cm–1: 1636, 1714,
1774, 1750. 1H NMR, δ: 2.29—2.68, 2.30—2.45 (both m,
2 H each, CH2); 3.59 (s, 3 H, Me); 3.99 (s, 2 H, BrCH2);
5.11—5.19 (m, 1 H, CH); 7.71—7.96 (m, 4 H, C6H4). 13C NMR,
δ: 23.3, 30.2, 30.9, 51.6, 55.4, 123.7, 131.4, 134.5, 167.5,
172.3, 196.4.
1,7ꢀBisdiazoꢀ3ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ
2,6ꢀdioxoheptane (10). Phosphorus pentachloride (10 g,
50 mmol) was added to a suspension of acid 1 (5.54 g, 20 mmol)
in dry CCl4 (100 mL). The reaction mixture was refluxed until
gas evolution ceased (~3 h) and cooled to room temperature.
Synthesis of sulfonium salts (general procedure). Dimethyl
sulfide (3 mmol) was added to a stirred solution of bromo ketone
(1 mmol) in dry acetone (10 mL) and the mixture was kept
for 12 h. The solvent was decanted and the precipitate was
washed with acetone.

Sulfur ylides from Nꢀphthalylglutamic acid
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 12, December, 2005 2871
5ꢀ[(1,3ꢀDioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀmethoxyꢀ
carbonylꢀ2ꢀoxopentyl]dimethylsulfonium bromide (5). The yield
was 61%, m.p. 153—155 °C. Found (%): C, 47.46; H, 4.15;
Br, 18.78; N, 3.28; S, 7.66. C17H20BrNO5S. Calculated (%):
C, 47.45; H, 4.68; Br, 18.57; N, 3.26; S, 7.45. IR, ν/cm–1: 1714,
1724, 1776. 1H NMR (CF3COOH), δ: 2.82 (s, 6 H, Me);
2.24—2.57, 2.65—2.81 (both m, 2 H each, CH2); 3.63 (s, 3 H,
Me); 4.55 (s, 2 H, CH2); 4.8—4.89 (m, 1 H, CH); 7.58—7.75
(m, 4 H, C6H4). 13C NMR, δ: 22.5, 24.7, 37.4, 51.3, 53.6, 54.4,
124.3, 130.9, 135.6, 169.9, 171.8, 200.5.
Intramolecular cyclization. An ylide (2 mmol) was dissolved
in hot dry toluene (8 mL). Then BzOH (2 mmol) was added and
the mixture was refluxed for 0.5 h. The solvent was removed and
the residue was chromatographed.
Methyl 2ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ6ꢀ
methylsulfanylꢀ5ꢀoxohexanoate (7). The yield was 19%.
Found (%): C, 57.25; H, 5.74; N, 4.84; S, 8.8. C16H17NO5S.
Calculated (%): C, 57.3; H, 5.11; N, 4.18; S, 9.56. IR, ν/cm–1
:
1721, 1733, 1765. 1H NMR, δ: 2.02 (s, 3 H, Me); 2.39—2.73,
2.52—2.65 (both m, 2 H each, CH2); 3.11 (s, 2 H, CH2); 3.72 (s,
3 H, Me); 4.85—4.95 (m, 1 H, CH); 7.69—7.88 (m, 4 H, C6H4).
13C NMR, δ: 15.5, 23.0, 36.1, 42.5, 51.0, 52.7, 123.5, 131.6,
134.2, 167.4, 169.2, 203.5.
1,7ꢀBis(dimethylsulfonio)ꢀ3ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀ
isoindolꢀ2ꢀyl)ꢀ2,6ꢀdioxoheptane dibromide (12). The yield was
70% (hygroscopic compound). Found (%): C, 41.6; H, 4.95;
Br, 28.05; N, 2.35; S, 10.8. C17H20BrNO5S. Calculated (%):
Methyl 6ꢀbenzoyloxyꢀ2ꢀ(1,3ꢀdioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ
2ꢀyl)ꢀ5ꢀoxohexanoate (8). The yield was 32%. Found (%):
C, 64.29; H, 4.91; N, 2.93. C22H19NO7. Calculated (%):
C, 64.55; H, 4.68; N, 3.42. IR, ν/cm–1: 1718, 1729, 1778.
1H NMR, δ: 2.39—2.73, 2.52—2.65 (both m, 2 H each, CH2);
3.72 (s, 3 H, Me); 4.82 (s, 2 H, CH2); 4.85—4.95 (m, 1 H, CH);
7.41 (t, 2 H, mꢀHPh, J = 7.6 Hz); 7.55 (t, 1 H, pꢀHPh, J =
7.6 Hz); 7.41 (d, 2 H, oꢀHPh, J = 7.6 Hz); 7.69—7.88 (m, 4 H,
C6H4). 13C NMR, δ: 22.5, 35.1, 50.9, 52.7, 68.1, 123.5, 128.3,
128.9, 129.7, 131.5, 133.3, 134.2, 165.6, 167.4, 169.0, 202.4.
2ꢀ(2,5ꢀDioxocycloheptꢀ3ꢀenyl)isoindoleꢀ1,3(2H )ꢀdione (14).
The yield was 40%. Found (%): C, 66.69; H, 3.98; N, 5.21.
C15H11NO4. Calculated (%): C, 66.91; H, 4.12; N, 5.2. IR,
C, 41.09; H, 4.54; Br, 28.78; N, 2.52; S, 11.55. IR, ν/cm–1
:
1
1714, 1724, 1776. H NMR (CF3COOH), δ: 2.83 (s, 6 H, Me);
2.39—2.59, 2.52—2.81 (both m, 2 H each, CH2); 4.52, 4.78
(both s, 2 H each, CH2); 4.85—5.08 (m, 1 H, CH); 7.58—7.72
(m, 4 H, C6H4). 13C NMR, δ: 25.1, 29.5, 37.7, 53.4, 54.5, 57.4,
124.6, 131.0, 135.9, 169.6, 196.1, 200.5.
3ꢀ[(1,3ꢀDioxoꢀ2,3ꢀdihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀmethoxyꢀ
carbonylꢀ2ꢀoxopentyl]dimethylsulfonium bromide (18). The yield
was 69%, m.p. 130—132 °C. Found (%): C, 46.89; H, 4.16;
Br, 18.71; N, 3.56; S, 7.91. C17H20BrNO5S. Calculated (%):
C, 47.45; H, 4.68; N, 3.26; Br, 18.57; S, 7.45. IR, ν/cm–1: 1714,
1724, 1776. 1H NMR (CF3COOH), δ: 2.82 (s, 6 H, Me);
2.24—2.57, 2.65—2.81 (both m, 2 H each, CH2); 3.63 (s, 3 H,
Me); 4.55 (s, 2 H, CH2); 4.80—4.89 (m, 1 H, CH); 7.58—7.75
(m, 4 H, C6H4). 13C NMR, δ: 22.5, 24.7, 37.4, 51.3, 53.6, 54.4,
124.3, 130.9, 135.6, 169.9, 171.8, 200.5.
1
ν/cm–1: 1753, 1758, 1765. H NMR, δ: 2.12—3.11, 2.83—2.98
(both m, 2 H each, CH2); 4.97—4.06 (m, 1 H, CH); 6.55 (s,
2 H, CH=CH); 7.68—8.28 (m, 4 H, C6H4). 13C NMR, δ: 24.6,
40.8, 58.7, 123.6, 131.7, 134.3, 135.3, 137.6.
Synthesis of sulfur ylides by deprotonation of sulfonium salts
(general procedure). Sodium hydride (1.1 mmol) was added in
one portion to a stirred suspension of a sulfonium salt (3 mmol)
in anhydrous THF (10 mL). The reaction mixture was stirred for
30 min, filtered, dried over K2CO3, and concentrated. All the
ylides obtained are very unstable and decompose at room temꢀ
perature.
Methyl 3ꢀ[1ꢀ(methylthio)ꢀ2,5ꢀdioxoꢀ2,5ꢀdihydroꢀ3Hꢀpyrꢀ
rolo[2,1ꢀa]isoindolꢀ3ꢀyl]propanoate (20). The yield was 56%.
Found (%): C, 59.93; H, 5.34; N, 4.44; S, 10.01. C16H15NO4S.
Calculated (%): C, 60.56; H, 5.76; N, 4.41; S, 10.10. IR, ν/cm–1
:
1720, 1734, 1765. 1H NMR, δ: 2.19 (s, 3 H, Me); 2.32—2.65,
2.49—2.61 (both m, 2 H each, CH2); 3.64 (s, 3 H, Me);
4.45—4.54 (m, 1 H, CH); 7.68—8.28 (m, 4 H, C6H4). 13C NMR,
δ: 15.6, 25.8, 29.2, 51.7, 60.6, 122.1, 124.3, 125.3, 130.2, 132.3,
132.8, 133, 161.8, 162.2, 172.6, 199.1.
4
Methyl 6ꢀ(dimethylꢀλ ꢀsulfanylidene)ꢀ2ꢀ(1,3ꢀdioxoꢀ2,3ꢀ
dihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀoxohexanoate (6). The yield
was 86%. Found (%): C, 58.77; H, 5.01; N, 3.99; S, 9.2.
C17H19NO5S. Calculated (%): C, 58.44; H, 5.48; N, 4.01;
S, 9.18. IR, ν/cm–1: 1560, 1714, 1774.
This work was financially supported by the Presidium
of the Russian Academy of Sciences (Program for Basic
Research "Targeted Synthesis of Organic Compounds with
Desired Properties and Creation of Functional Materials
on Their Basis") and the Council on Grants of the Presiꢀ
dent of the Russian Federation (Program for State Supꢀ
port of Leading Scientific Schools of the Russian Federaꢀ
tion, Grant NShꢀ139.2003.3).
4
2ꢀ[1,7ꢀBis(dimethylꢀλ ꢀsulfanylidene)ꢀ2,6ꢀdioxoheptanꢀ3ꢀ
yl]ꢀ2Hꢀisoindoleꢀ1,3ꢀdione (13). The yield was 45%. Found (%):
C, 58.04; H, 5.33; N, 3.6; S, 16.35. C19H23NO4S2. Calcuꢀ
lated (%): C, 57.99; H, 5.89; N, 3.56; S, 16.29. IR, ν/cm–1
:
1540 (br), 1714, 1774.
4
Methyl 6ꢀ(dimethylꢀλ ꢀsulfanylidene)ꢀ4ꢀ(1,3ꢀdioxoꢀ2,3ꢀ
dihydroꢀ1Hꢀisoindolꢀ2ꢀyl)ꢀ5ꢀoxohexanoate (19). The yield
was 82%. Found (%): C, 58.98; H, 4.85; N, 3.76; S, 8.79.
C17H19NO5S. Calculated (%): C, 58.44; H, 5.48; N, 4,01;
S, 9.18. IR, ν/cm–1: 1560, 1714, 1774.
References
Synthesis of sulfur ylides according to the carbene method
(general procedure). The salt Rh2(OAc)4 (0.004 g, 0.009 mmol)
was added in one portion to a stirred solution of diazo ketone
(2.05 mmol) and Me2S (1.0 g, 16.1 mmol) in dry benzene
(10 mL). The reaction mixture was stirred at 80 °C until
the diazo ketone disappeared (TLC, CHCl3—Me2CO (9 : 1),
spot visualization with ninhydrin). The solvent was removed,
toluene was added, and intramolecular cyclization was carꢀ
ried out.
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Received June 21, 2005;
in revised form October 21, 2005