α-Sulfonyl succinimides: Versatile sulfinate donors in Fe-catalyzed, salt-free, neutral allylic substitution

Article abstract of DOI:10.1002/chem.201101047

Allyl sulfones are versatile intermediates in organic chemistry. The presence of two distinct functional groups sets the stage for a plethora of subsequent transformations. However, despite these advantages the preparation of regioisomerically enriched sulfones is not easy. The use of sulfinate salts as nucleophiles in substitutions is frequently accompanied by side reactions such as π-bond migration, β-elimination, and so on. Herein we present a preparatively simple way to synthesize a variety of different aryl or alkyl allyl sulfones starting from readily accessible allylic carbonates. By employing aryl or alkyl α-sulfonyl succinimides as sulfinate synthons, mild and regioselective ipso substitution of diverse allylic carbonates was realized.

Full text of DOI:10.1002/chem.201101047

FULL PAPER
DOI: 10.1002/chem.201101047
a-Sulfonyl Succinimides: Versatile Sulfinate Donors in Fe-Catalyzed, Salt-
Free, Neutral Allylic Substitution
Markus Jegelka and Bernd Plietker*[a]
Abstract: Allyl sulfones are versatile
intermediates in organic chemistry. The
presence of two distinct functional
groups sets the stage for a plethora of
subsequent transformations. However,
despite these advantages the prepara-
tion of regioisomerically enriched sul-
fones is not easy. The use of sulfinate
salts as nucleophiles in substitutions is
frequently accompanied by side reac-
tions such as p-bond migration, b-elim-
ination, and so on. Herein we present a
preparatively simple way to synthesize
a variety of different aryl or alkyl allyl
sulfones starting from readily accessi-
ble allylic carbonates. By employing
aryl or alkyl a-sulfonyl succinimides as
sulfinate synthons, mild and regioselec-
tive ipso substitution of diverse allylic
carbonates was realized.
Keywords: allylic compounds
iron sulfones sulfonylation
synthetic methods
·
·
·
·
Introduction
cleophilic displacement faces regioselectivity problems in
the case of allylic leaving groups, the latter method is a two-
step protocol that involves the use of hazardous reagents.
Furthermore, allylic thioethers are prone to undergo radical
isomerization.[24]
Sulfones are an important subclass of organosulfur com-
pounds. They can be regarded as S analogues of carbonyl
compounds and hence have reactivities that are somewhat
comparable.[1] A variety of functional-group transformations
using sulfones as auxiliaries have been published. The fact
that the sulfone group can also serve as a leaving group
opens up novel strategies for direct functionalization of C
H bonds. Hence, reductive, oxidative, or methylenating de-
sulfurization allows for transformation of the C S bond into
a C H, C O, or C=C bond. Furthermore, sulfones are im-
portant intermediates in olefination processes such as the
Julia–Kocienski, Julia–Lythgoe, and Ramberg–Bꢀcklund re-
actions. Using the a-sulfonyl anion in Michael-type addi-
tions to a,b-unsaturated carbonyl compounds led to desul-
furization with concomitant formation of a cyclopropane
unit. The implementation of further proximal functional
groups such as olefins expands the scope of application sig-
nificantly (Scheme 1).[2–21]
Transition metal complexes are an interesting alternative
for direct nucleophilic displacement of allylic leaving groups
for a sulfonyl moiety, a field that was long dominated by the
use of Pd catalysts.[25] The dynamic character of the inter-
mediate fluxional allyl metal species in combination with
the use of chiral ligands allows for good to high levels of
asymmetric induction,[25] but in most cases strict control of
the regioselectivity is still problematic. Hartwig et al.
showed that this problem can in part be overcome by using
Ir complexes.[26,27] Independent of the structure of the start-
ing material, excellent levels of regio- and stereocontrol
were observed in favor of the branched sulfone having a
monosubstituted olefin. Complementary to this method, cat-
alytic protocols for the regioselective ipso substitution of al-
lylic carbonates based on Rh[28] and Fe complexes[29] were
ꢀ
ꢀ
ꢀ
ꢀ
Due to the versatility of sulfones as building blocks in or-
ganic synthesis, a variety of methods for their preparation
has been developed. The most commonly used transforma-
tions are replacement of a leaving group (halide, sulfonate,
etc.) by nucleophilic displacement[22] and Mitsunobu-type
exchange of a hydroxyl group for a mercapto substituent fol-
lowed by oxidation to the corresponding sulfone.[23] Both
protocols are hampered by synthetic problems. Whereas nu-
reported
recently.
Nucleophilic
Fe
complex
Bu4N[Fe(CO)3(NO)] (TBAFe) allows for regio- and stereo-
ꢀ
ꢀ
ꢀ
conserving exchange of an allylic C O for a C C, or C N
bond. Furthermore, good levels of regio- and stereoselectiv-
ity were observed in the corresponding allylic sulfonylation
using aryl sulfinates as nucleophiles.[29e] However, this
method proved to be restricted to the formation of primary
and tertiary aryl sulfones.
Whereas aliphatic sulfinates proved to be unreactive, sec-
ondary sulfones were shown to undergo an undesired shift
of the double bond to give the corresponding vinyl sulfones.
Moreover, the existing methodologies for transition metal
catalyzed allylic sulfonylation are restricted to the use of
simple unfunctionalized sulfinate salts. This fact is not a con-
sequence of an incompatibility of functionalized sulfinates
with the metal catalysts, but rather due to a lack of reactive
[a] Dipl.-Chem. M. Jegelka, Prof. Dr. B. Plietker
Institut fꢁr Organische Chemie
Universitꢀt Stuttgart, Pfaffenwaldring 55
70569 Stuttgart (Germany)
Fax : (+49)711-68564285
E-mail: bernd.plietker@oc.uni-stuttgart.de
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/chem.201101047.
Chem. Eur. J. 2011, 17, 10417 – 10430
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Scheme 1. Allylic sulfones: versatile building blocks in organic chemistry.
sulfinate surrogates. Here we summarize the results of an
in-depth study which finally led to the development of salt-
free, Fe-catalyzed regioselective allylic sulfonylation using
readily available functionalized a-sulfonyl succinimides as
pronucleophiles. With this species in hand, a variety of allyl,
alkyl, aryl, and heteroaromatic sulfonyl groups are allylated
with moderate to excellent levels of regio- and stereoconser-
vation.
Results and Discussion
As noted above, undesired p-bond isomerization and the
strict limitation to aryl sulfinates are serious synthetic draw-
backs that needed to be addressed. We envisioned two fac-
tors to be a source for these problems. Firstly, the use of
preformed nucleophiles (the aryl sulfinates were employed
as their sodium salts) leads to formation of free base in each
catalytic cycle and hence may be the reason for the base-
promoted isomerization reaction. Secondly, the established
procedures for preparation of sulfinates do not allow for the
preparation of functionalized sulfinates. To circumvent both
problems we wondered whether in situ generation of reac-
tive sulfinate by base-promoted b-elimination would solve
the problem of p-bond isomerization, since the leaving
group would serve as a base generated in situ (Scheme 2).
We prepared different potential sulfinate donors by a
two-step procedure of Michael addition of a mercaptan and
Scheme 2. Neutral allylic sulfonylation with sulfinates generated in situ.
subsequent oxidation of the thioether to the corresponding
sulfone (Scheme 3). b-Sulfonyl butanone 3 was recently re-
ported to be a versatile precursor for the preparation of sul-
finate and served as a prototype for a sulfinate donor.[30]
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a-Sulfonyl Succinimides
FULL PAPER
Allyl carbonate 10 was trans-
formed into corresponding allyl
sulfone 11 with almost full con-
version and good regioselectivi-
ty in favor of ipso substitution
product 11-A. Subjecting secon-
dary carbonate 12 to the reac-
tion conditions gave desired
product 13 in good yields, albeit
with moderate regioselectivities
and significant amounts of vinyl
sulfone 13-D (Table 2). Al-
though the addition of water as
a cosolvent suppressed the p-
bond isomerization to some
extent (Table 2, entry 2), this
undesired side reaction was ob-
Scheme 3. Preparation of potential sulfinate donors.
Table 1. Influence of solvent and temperature.[a]
Table 2. Influence of solvent.[a]
Entry
Solvent
11-A:11-B[b]
Conv. [%][c]
Entry Solvent
Conv. [%][b] 13-A:13-B:13-C:13-D[c]
1
2
3
4
5
6
7
DMF/MeOC2H4OH
THF
MTBE
91:9
96:4
97:3
94:6
95:5
96:4
97:3
29
29
96
50
39
15
27
AHCTUNGTRENNUNG
1
2
MTBE (500 mL)
36:12:1:50
75:7:1:18
DMF
AHCTUNGTRENNUNG
acetonitrile
butanone
n-hexane
3
4
iBuOH (250 mL)
tBuOH (250 mL)
94 (17 h)
93 (3 days)
69:18:3:10
50:18:1:31
[a] Reactions were performed on a 0.5 mmol scale with sulfinate donor 3
(1 equiv), TBAFe (5 mol%), and PPh3 (6 mol%) in the given solvent at
808C. [b] Determined by GC integration of the crude reaction mixture
with dodecane as internal standard. [c] Determined by GC integration of
the crude reaction mixture.
[a] Reactions were performed under an N2 atmosphere on a 0.5 mmol
scale with sulfinate donor 3 (1 equiv), TBAFe (5 mol%), and PPh3
(6 mol%) in the given solvent (0.5 mL) at 808C and stopped after 24 h.
[b] Determined by GC integration of the crude reaction mixture. [c] De-
termined by GC integration of the crude reaction mixture with dodecane
as internal standard.
served over the prolonged reaction times in alcoholic sol-
vents (Table 2, entry 3). At this point an in depth ligand
screening was performed (Table 3).
Maleic acid-derived sulfinate donors 6 and 9 were chosen as
alternative pronucleophiles, since they open the chance for
potential immobilization and hence for a regeneration of
the sulfonylating agent. When commercially unavailable
thiols are used, a procedure of Kotake et al. can be em-
ployed for synthesis of thioethers.[34] By employing thiosac-
As previously observed,[29e] p-methoxy triaryl phosphine
15 proved to be the best ligand, resulting in clean formation
of products 13 in good yield. However, the improved yield is
at the expense of p-bond isomerization. Apparently, the nu-
cleophilicity of the catalyst combination of TBAFe/P ligand
is not sufficient for a fast reaction. The use of more electron
rich N-heterocyclic carbene ligands (NHC) might increase
the nucleophilicity. To suppress undesired reactions between
ligand and protic solvent we initially tested several NHC li-
gands, employing methyl tert-butyl ether (MTBE) as an
aprotic solvent that was shown to be suitable for TBAFe-
catalyzed allylic substitutions in earlier investigations (Ta-
ble 4).[29c,d]
ꢀ
charine, the C S bond in the desired thiols is formed on nu-
cleophilic substitution. Cleavage of the resulting thioether in
the presence of maleimide 7 gives thioethers of type 8 in a
one-pot fashion.
Initial experiments focused on the use of methyl vinyl
ketone derived sulfone 3 as a pronucleophilic sulfinate
donor. The previously established standard allylation condi-
tions for salt-free allylic substitutions were chosen as a start-
ing point with allyl carbonate 10 as test substrate (Table 1).
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10419

B. Plietker and M. Jegelka
Table 3. Ligand screening: P ligands.[a]
Table 4. Ligand screening: carbene ligands.[a]
Yield [%][b] 13-A:13-B:13-C:13-D[c]
Entry
Carbene
ligand
Yield
[%][e]
13-A:13-B:13-C:13-D[f]
Entry P ligand
1[b]
65
44:41:3:13
1
2
3
14 (R=CH3)
15 (R=OCH3)
16 (R=Cl)
80
88
<10
69:16:3:12
54:17:4:24
n.d.
2[c]
6
62:20:3:15
4
5
6
7
8
84
38:13:2:47
n.d.
<10
79
52:12:2:34
n.d.
3[b]
35
44:53:3:n.d.
traces
61
4[b]
5[b]
26
16
71:22:3:5
86:11:1:2
52:16:2:29
6[b]
99
4:53:6:37
9
35
40
72:16:4:9
7[d]
98
81:14:2:3
10
75:13:2:10
[a] Reactions were performed on a 0.5 mmol scale in iBuOH (0.25 mL)
with sulfinate donor 3 (1 equiv), TBAFe (5 mol%), and the given ligand
(6 mol%) at 808C and were stopped after 14 h. [b] Determined by GC
integration of the crude reaction mixture with dodecane as internal stan-
dard. [c] Determined by GC integration of the crude reaction mixture.
[a] Reactions were performed on a 0.5 mmol scale in MTBE (0.5 mL)
with sulfinate donor 3 (1 equiv), TBAFe (5 mol%), and the given NHC
ligand (5 mol%) at 808C and were stopped after 14 h. [b] Ligands were
generated from their BF4 or PF6 salts by using KOtAm in MTBE at
608C. [c] Ligand generated from neutral precursor using KOtAm in
MTBE at 608C. [d] Ligand generated thermally in a microwave reactor
(MTBE, 808C, 30 min) from its CHCl3 adduct. [e] Determined by GC in-
tegration of the crude reaction mixture with dodecane as internal stan-
dard. [f] Determined by GC integration of the crude reaction mixture.
Whereas most of the NHC ligands did not show any sig-
nificant improvement, mesityl-substituted NHC ligand 1,3-
bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMES, 29)
gave a first positive indication (Table 4, entry 6). However,
although the yields were almost quantitative, the regioselec-
tivity and p-bond stability were poor. To investigate the role
of the counteranion and/or added base we finally employed
the chloroform adduct of ligand 29, SIMES·CCl3 (30),[31] and
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a-Sulfonyl Succinimides
FULL PAPER
were surprised to find that base-free, thermal liberation of
the SIMES ligand allowed for full conversion and reasona-
ble regioselectivity (Table 4, entry 7). More importantly,
almost no p-bond isomerization was detected. At this point
the influence of the sulfinate donor was investigated
(Table 5).
that might be envisioned due to the use of a nucleophilic
carbene in protic solvents were not observed.
Subsequently, different substituted sulfinate donors 31–39
were prepared and subjected to the reaction conditions
using carbonate 10 as the allylating agent (Table 6). The
Table 6. Iron-catalyzed allylic sulfonylation: scope of sulfinate donors.[a]
Table 5. Influence of the sulfinate donor.[a]
Entry
1
Sulfinate
donor
Yield
[%][b]
13-A:13-B:13-C:13-D[c]
Entry
1
R
Sulfinate
donor
Product
AHCTUNGTRENNUNG
(A:B)[b]
Yield
[%][c]
96
81:14:2:3
31
40 (94:6)
87
2
3
100
89:5:2:3
91:5:1:3
2
3
32
33
41 (96:4)
42 (92:8)
83
71
17
4
5
6
34
35
36
43 (97:3)
44 (98:2)
45 (94:6)
86
81
81
[a] Reactions were performed on a 0.5 mmol scale in MTBE (0.5 mL)
with the given sulfinate donor (1 equiv), TBAFe (5 mol%), and SIMES
(5 mol%, generated thermally from SIMES·CCl3 in a microwave reactor)
at 808C and were stopped after 6 h. [b] Determined by GC integration of
the crude reaction mixture with dodecane as internal standard. [c] Deter-
mined by GC integration of the crude reaction mixture.
7
8
37
38
46 (92:8)
47 (94:6)
84
54
Maleimide-derived sulfinate donor 9 proved to be superi-
or to the other tested substrates. The corresponding sulfony-
lation product 13 was formed in quantitative yield and good
regioselectivity in favor of ipso substitution product 13-A.
p-Bond isomerization was almost undetectable. Fine-tuning
of solvent and temperature finally led to a protocol that al-
lowed sulfonylation at 408C with only 5 mol% of iron cata-
lyst and 5 mol% of SIMES·CCl3. The desired product 13-A
was obtained in high yield with good ipso selectivity and no
p-bond isomerization (Scheme 4). Furthermore, this reac-
tion shows that NHC ligands like SIMES can be employed
for reactions in alcoholic solvents. Undesired side reactions
9
39
48 (94:6)
54
[a] Reactions were performed on a 0.5 mmol scale in 2-methoxyethanol
(0.5 mL) with the given sulfinate donor (1 equiv), TBAFe (5 mol%), and
SIMES (5 mol%, generated thermally from SIMES·CCl3 in a microwave
reactor) at 408C. [b] Determined by GC or 1H NMR integration of the
crude product. [c] Yield of isolated product.
concept of generating the active sulfinate in situ proved to
be broadly applicable. A variety of different aromatic and
aliphatic allyl sulfones 40–48 were isolated in good to excel-
lent yields and regioselectivities. The method displays broad
tolerance of functional groups. Esters, ethers, and strained
carbocycles are tolerated (Table 6, entries 7–9). Heteroaro-
matic sulfones are important structural motifs that allow for
Julia–Kocienski-type olefination reactions. We wondered
whether this new sulfonylation method would also be appli-
cable to heteroaromatic sulfinate donors such as pyridyl de-
rivative 49, and found that corresponding allylic sulfone 50
was formed with 3:1 regioselectivity in favor of the ipso sub-
stitution product. p-Bond isomerization was not observed
(Scheme 5). However, although this sulfonylation reaction is
an interesting method for direct preparation of Julia–Ko-
Scheme 4. Regioselective allylic sulfonylation (yields of isolated products,
product composition determined by GC analysis).
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10421

B. Plietker and M. Jegelka
tion observed. Furthermore, the electronic nature of sub-
stituent R3 plays a crucial role in the reactivity of the start-
ing material. In general the transformations are slower in
the case of disubstituted C=C bonds. While electron-releas-
ing substituents like alkyl groups slow down the reaction, ꢀI
substituents such as aryl groups maintain the reactivity of
the starting material (Table 7, entries 7 and 8).
Apart from the regioselective course of this transforma-
ꢀ
tion, the stereoselectivity of C S bond formation is of simi-
Scheme 5. Preparation of heteroaromatic sulfones.
lar importance. To confirm that the stereochemical informa-
tion is conserved in the catalytic process, enantiomerically
enriched (R)-linalyl carbonate 60 was subjected to the stan-
dard sulfonylation conditions, and desired product 61 was
obtained with good enantiomeric purity in high yield
cienski-type olefination precursors, the moderate regioselec-
tivity must be improved in future work.
ꢀ
Having found a suitable sulfinate donor, we investigated
the regioselective course of the allylation using different al-
lylic carbonates. Apart from regioselectivity, p-bond isomer-
ization was another focus of these studies (Table 7). Various
allylic carbonates were sulfonylated in moderate to good
yields and regioselectivities. The regioselectivities observed
in this study clearly point to a p-allyl mechanism.[29c] The
amount of the sterically less hindered product increased
with increasing size of substituent R1 (Table 7, entries 1, 2, 5,
and 6). Another driving force for a change in the regioselec-
tivity is the preferred formation of the regioisomer in which
the C=C-bond is in conjugation with unsaturated substitu-
ents (Table 7, entries 3 and 7–10). The preference for a p-
allyl mechanism when SIMES is used as ligand is in line
with our previous observations in the corresponding allylic
alkylation.[29c,d] However, in no case was p-bond isomeriza-
(Scheme 6). The new C S bond was formed with a high
preference for the ipso-substitution product (>92%) and
almost perfect retention of configuration. Test experiments
with the same system in the absence of sulfone 9 revealed
configurational stability of the allylic carbonate under the
reaction conditions.
Scheme 6. Stereochemical course of the allylic sulfonylation (yields of
isolated products, e.r. determined by chiral HPLC analysis).
Table 7. Iron-catalyzed allylic sulfonylation: scope of allylic carbonates.[a]
Conclusion
We have reported broadly applicable, practical, iron-cata-
lyzed allylic sulfonylation under salt-free and neutral reac-
tion conditions at slightly elevated temperature of 408C in
short reaction times. The use of an a-sulfonyl succinimide as
a sulfinate donor that liberates the sulfinate by base-mediat-
ed b-elimination is the key feature of this protocol. A varie-
ty of functionalized aromatic, heteroaromatic, and aliphatic
sulfinate donors were prepared and successfully employed
in the allylation process. Although the regioselectivity of the
allylation reaction needs to be improved in future studies,
the good reactivity of the readily accessible a-sulfonyl succi-
nimides and the lack of any p-bond isomerization may open
a new synthetic pathway for the preparation of functional-
ized allylic sulfones as building blocks in organic synthesis.
Entry
R1
R2
R3
Product
AHCTUNGTRENNUNG
(A:B)[b]
Yield
[%][c]
1
2
3
4
5
6
7
8
CH3
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Ph
CH3
Ph
H
51 (91:9)
52 (79:21)
53 (59:41)
54 (9:91)
55 (50:50)
56 (61:39)
57 (81:19)
57 (19:81)
53 (77:23)
58 (1:99)
59 (ꢀ)
86
81
23
42
30
62
83
39
44
52
88
A
Ph
CO2CH3
CH
CH2OCH2Ph
CH3
Ph
H
Ph
Me
(CH3)2
9
10
11
H
CO2C
H
ACHTUGNTERN(NUNG CH3)3
Me
Experimental Section
[a] Reactions were performed on a 0.5 mmol scale in 2-methoxyethanol
(0.5 mL) with sulfinate donor 31 (1 equiv), TBAFe (5 mol%), and
SIMES (5 mol%, generated thermally from SIMES·CCl3 in a microwave
reactor) at 408C. [b] Determined by GC or 1H NMR integration of the
crude product. [c] Yield of isolated product.
General remarks: All reactions and manipulations which are sensitive to
air or moisture were performed under dry nitrogen by using standard
Schlenk techniques. All solvents were purified prior to use. All chemicals
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a-Sulfonyl Succinimides
FULL PAPER
were purchased from Acros Organics, Sigma Aldrich, or Alfa Aesar. GC
experiments were conducted on a Thermo Finnigan Focus GC with do-
decane as internal standard. Microwave experiments were conducted in a
CEM Discovery microwave reactor. NMR spectra were recorded on a
Bruker AV300 spectrometer at 300 MHz (1H NMR), 75 MHz (13C NMR)
or a Bruker AV500 spectrometer at 500 MHz (1H NMR), 125.6 MHz
(13C NMR). Chemical shifts are reported in ppm downfield versus tetra-
methylsilane as internal standard. Signals are indicated as s (singlet), d
(doublet), t (triplet), q (quartet), m (multiplet), or mc (multiplet cen-
tered). IR spectra were measured on a Bruker Vector 22 FTIR spectrom-
eter in ATR mode. Mass spectra were measured on a GC-MS HP6890 or
on a Bruker Micro-TOF-Q. Thiosaccharine sodium salt,[32] N-phenylma-
1-Phenyl-3-(phenylsulfonyl)pyrrolidine-2,5-dione (9): Sulfone 9 was pre-
pared according to GPIII. After recrystallization from ethanol the prod-
uct was obtained as a white solid (2.54 g, 8.1 mmol, 84% yield). Rf =0.39
(petroleum ether/ethyl acetate 1/1); m.p. 190–1928C; 1H NMR
(300 MHz, CDCl3): d=8.00–7.94 (m, 2H; Ar-H), 7.76 (t, J=7.5 Hz, 1H;
Ar-H), 7.66–7.59 (m, 2H; Ar-H), 7.50–7.37 (m, 3H; Ar-H), 7.20–7.13 (m,
2H; Ar-H), 4.48 (dd, J=9.7, 3.7 Hz, 1H; SO2CH), 3.56 (dd, J=19.3,
3.7 Hz, 1H; SO2CHCH2), 3.26 ppm (dd, J=19.3, 9.7 Hz, 1H;
SO2CHCH2); 13C NMR (75 MHz, CDCl3): d=171.9 (C=O), 167.7 (C=O),
136.4 (Ar-C), 135.1 (Ar-C), 131.0 (Ar-C), 129.6 (2C; Ar-C), 129.5 (2C;
Ar-C), 129.3 (2C; Ar-C), 129.2 (Ar-C), 126.3 (2C; Ar-C), 63.6 (SO2CH),
~
29.2 ppm (SO2CHCH2); IR (neat): n=3000, 2943, 1778, 1710, 1594, 1584,
[31]
leimide,[33] Bu4N[Fe(CO)3NO],[29d] and SIMES·CCl3 were prepared ac-
1498, 1447, 1390, 1332, 1322, 1308, 1197, 1179, 1157, 1135, 1084, 1072,
1030, 999, 928, 797, 760, 689 cmꢀ1; MS (EI, 70 eV): m/z (%): 316 (17)
[M+H+], 174 (6), 143 (2), 125 (2); HRMS (ESI): m/z calcd for
C16H13NO4S+Na: 338.0459, found: 338.0457.
cording to known methods.
General procedure for preparation of thioethers by thio Michael addition
(GPI): Thioethers were prepared according to a modified literature pro-
cedure from Kotake et al.[34] A solution of alkyl bromide or chloride in
DMF (3 mL) was added to a solution of thiosaccharine sodium salt
(1.11 g, 5 mmol) in DMF (3.5 mL) under N2 atmosphere at room temper-
ature. The solution was heated to 508C and stirred overnight. Then de-
ionized water was added to precipitate the product, which was collected
by filtration and recrystallized from ethanol. The obtained product
(3.5 mmol) was then dissolved in CH3CN (6 mL) under N2 atmosphere,
treated with a solution of piperidine (302 mg, 3.5 mmol) in CH3CN
(3 mL), and stirred for 30 min at room temperature. Then a solution of
N-phenylmaleimide (607 mg, 3.5 mmol) in CH3CN (9 mL) was added.
After stirring for 3 h at room temperature triethylamine (7 drops) was
added, and the mixture stirred for a further 1.5 h. The solvent was evapo-
rated and the residue purified by flash column chromatography.
3-(Benzylsulfonyl)-1-phenylpyrrolidine-2,5-dione (31): Thioether 31 was
prepared according to GPII and obtained as
a white solid (4.83 g,
16.2 mmol, 81% yield). Rf =0.21 (petroleum ether/ethyl acetate 3/1);
1
m.p. 141–1428C; H NMR (300 MHz, CDCl3): d=7.53–7.27 (m, 10H; Ar-
H), 4.29 (d, J=13.7 Hz, 1H; SCH2), 3.90 (d, J=13.7 Hz, 1H; SCH2), 3.65
(dd, J=9.5, 3.8 Hz, 1H; SCH), 3.16 (dd, J=18.9, 9.5 Hz, 1H; SCHCH2),
2.58 ppm (dd, J=18.9, 3.8 Hz, 1H; SCHCH2); 13C NMR (75 MHz,
CDCl3): d=175.7 (C=O), 173.7 (C=O), 136.7 (Ar-C), 131.6 (Ar-C), 129.3
(2C; Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C), 128.7 (2C; Ar-C), 127.6 (Ar-
C), 126.4 (2C; Ar-C), 37.2 (SC), 36.0 (SC), 35.5 ppm (SCHCH2); IR
~
(neat) n=3064, 3029, 2947, 1780, 1701, 1594, 1490, 1454, 1393, 1210,
1186, 1165, 1070, 1025, 928, 780, 749, 697, 630 cmꢀ1; MS (ESI): m/z (%):
320 (100) [M+Na+], 242 (1); HRMS (ESI): m/z calcd for C17H15 NO2S+
Na: 320.0716, found: 320.0695. The thioether was then oxidized to sul-
fone 31 according to GPIII. After recrystallization from EtOH the prod-
uct was obtained as a white solid (4.48 g, 13.6 mmol, 84% yield). Rf =
0.62 (petroleum ether/ethyl acetate 1/1); m.p. 174–1758C; 1H NMR
(300 MHz, CDCl3): d=7.67–7.28 (m, 10H; Ar-H), 4.98 (d, J=14.2 Hz,
1H; SO2CH2), 4.49 (d, J=14.2 Hz, 1H; SO2CH2), 4.28 (dd, J=9.9,
4.2 Hz, 1H; SO2CH), 3.41 (dd, J=19.2, 4.2 Hz, 1H; SO2CHCH2),
3.05 ppm (dd, J=19.2, 9.9 Hz, 1H; SO2CHCH2); 13C NMR (75 MHz,
CDCl3): d=171.9 (C=O), 169.2 (C=O), 137.4 (Ar-C), 135.2 (Ar-C), 131.3
(2C; Ar-C), 129.6 (Ar-C), 129.4 (2C; Ar-C), 129.3 (2C; Ar-C), 127.0 (Ar-
C), 126.5 (2C; Ar-C), 58.5 (SO2C), 56.9 (SO2C), 27.9 ppm (SO2CHCH2);
General procedure for the preparation of thioethers by thio Michael ad-
dition (GPII): A solution of mercaptan (20.2 mmol) was added to a solu-
tion of N-phenylmaleimide (20 mmol) and triethylamine (210 mL,
1.4 mmol) in benzene (35 mL) over 30 min. The solution was diluted with
benzene (20 mL) and stirred at room temperature over night. The solvent
was then evaporated and the resulting product washed with petroleum
ether (for solid products) and dried in vacuo.
General procedure for the oxidation of thioethers to sulfones (GPIII): A
solution of thioether (20 mmol) in dichloromethane (100 mL) was cooled
to 08C and meta-chloroperoxybenzoic acid (mCPBA; 70%, 10.4 g,
42 mmol) was added. After stirring for 10 min the solution was warmed
to room temperature and stirred for one hour. Then the solution was fil-
tered to remove the white precipitate, washed with a saturated Na2CO3
solution, dried over Na2SO4, filtered, and concentrated in vacuo. The re-
sulting product was purified by recrystallization from EtOH or column
chromatography.
~
IR (neat): n=3059, 2935, 1788, 1717, 1702, 1599, 1501, 1456, 1389, 1297,
1174, 1162, 1124, 1029, 932, 829, 798, 781, 748, 697, 635, 623, 613, 567,
544 cmꢀ1; MS (ESI): m/z (%): 352 (100) [M+Na+], 301 (1); HRMS
(ESI): m/z calcd for C17H15NO4S+Na: 352.0614, found: 352.9614.
3-(Naphthalen-1-ylmethylsulfonyl)-1-phenylpyrrolidine-2,5-dione
(32):
The thioether was prepared according to GPI and obtained after flash
column chromatography (petroleum ether/ethyl acetate gradient 10/1!5/
1) as a white solid (1.25 g, 3.6 mmol, 72% yield). Rf =0.19 (petroleum
ether/ethyl acetate 5/1); m.p. 121–1238C; 1H NMR (300 MHz, CDCl3):
d=8.18 (d, J=8.3 Hz, 1H; Ar-H), 7.92–7.80 (m, 2H; Ar-H), 7.63–7.28
(m, 9H; Ar-H), 4.73 (d, J=13.6 Hz, 1H; SCH2), 4.49 (d, J=13.6 Hz, 1H;
SCH2), 3.73 (dd, J=9.3, 3.8 Hz, 1H; SCH), 3.12 (dd, J=18.9, 9.32 Hz,
1H; SCHCH2), 2.53 ppm (dd, J=18.9, 3.8 Hz, 1H; SCHCH2); 13C NMR
(75 MHz, CDCl3) d=176.0 (C=O), 173.7 (C=O), 134.2 (Ar-C), 132.0 (Ar-
C), 131.6 (Ar-C), 131.3 (Ar-C), 129.3 (2C; Ar-C), 129.0 (Ar-C), 128.9
(Ar-C), 128.8 (Ar-C), 128.1 (Ar-C), 126.4 (3C; Ar-C), 126.1 (Ar-C), 125.2
(Ar-C), 123.9 (Ar-C), 37.8 (SC), 35.4 (SC), 33.8 ppm (SCHCH2); IR
General procedure for the oxidation of thioethers to sulfones (GPIV): A
solution of oxone (2.8 g, 4.5 mmol) in demineralized water was added to
a suspension of the thioether (1.5 mmol) in methanol (30 mL). The reac-
tion mixture was stirred over night and extracted with ethyl acetate. The
combined organic phases were dried over Na2SO4, filtered, and the sol-
vent evaporated in vacuo. The residue was purified by chromatography
on silica gel.
1-Phenyl-3-(phenylthio)pyrrolidine-2,5-dione (8): Thioether 8 was pre-
pared according to GPII and obtained as a white solid (2.74 g, 9.6 mmol,
96% yield). Rf =0.29 (petroleum ether/ethyl acetate 3/1); m.p. 191–
1928C; 1H NMR (300 MHz, CDCl3): d=7.62–7.56 (m, 2H; Ar-H), 7.48–
7.33 (m, 6H; Ar-H), 7.09–7.03 (m, 2H; Ar-H), 4.16 (dd, J=9.2, 3.8 Hz,
1H; SCH), 3.34 (dd, J=18.8, 9.2 Hz, 1H; SCHCH2), 2.92 ppm (dd, J=
18.8, 3.8 Hz, 1H; SCHCH2); 13C NMR (75 MHz, CDCl3): d=174.5 (C=
O), 173.5 (C=O), 135.2 (2C; Ar-C), 131.5 (Ar-C), 129.8 (Ar-C), 129.7
(Ar-C), 129.5 (2C; Ar-C), 129.2 (2C; Ar-C), 128.3 (Ar-C), 126.3 (2C; Ar-
~
(neat): n=3055, 2935, 1781, 1703, 1594, 1498, 1454, 1393, 1205, 1184,
1075, 1018, 948, 929, 793, 777, 750, 695, 629 cmꢀ1; MS (ESI): m/z (%):
370 (100) [M+Na+], 303 (5), 279 (2), 242 (10), 226 (44), 201 (2), 158 (2),
141 (64); HRMS (ESI): m/z calcd for C21H17NO2S+Na: 370.0872, found:
370.0864. The thioether was then oxidized to sulfone 32 according to
GPIII. After column chromatography (petroleum ether/ethyl acetate 1/1)
the product was obtained as a white solid (400 mg, 1.05 mmol, 70%
yield). Rf =0.60 (petroleum ether/ethyl acetate 1/1); m.p. 198–1998C;
1H NMR (300 MHz, CDCl3): d=8.28 (d, J=8.3 Hz, 1H; Ar-H), 7.95 (d,
J=8.1 Hz, 1H; Ar-H), 7.92 (d, J=8.5 Hz, 1H; Ar-H), 7.87 (d, J=7.1 Hz,
1H; Ar-H), 7.67–7.44 (m, 6H; Ar-H), 7.38–7.32 (m, 2H; Ar-H), 5.40 (d,
J=14.7 Hz, 1H; SO2CH2), 5.17 (d, J=14.7 Hz, 1H; SO2CH2), 4.50 (dd,
~
C), 44.2 (SCH), 36.4 ppm (SCHCH2); IR (neat): n=3471, 3063, 2931,
1777, 1705, 1594, 1573, 1497, 1473, 1456, 1440, 1390, 1303, 1290, 1277,
1198, 1157, 1069, 1024, 1003, 942, 922, 778, 737, 694 cmꢀ1; MS (ESI): m/z
(%): 306 (100) [M+Na+], 284 (42) [M+H+], 174 (9), 163 (2), 146 (14),
139 (5); HRMS (ESI): m/z calcd for C16H13NO2S+Na: 306.0559, found:
306.0570.
Chem. Eur. J. 2011, 17, 10417 – 10430
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10423

B. Plietker and M. Jegelka
J=9.8, 4.2 Hz, 1H; SO2CH), 4.41 (dd, J=19.3, 4.2 Hz, 1H; SO2CHCH2),
3.03 ppm (dd, J=19.3, 9.8 Hz, 1H; SO2CHCH2); 13C NMR (125 MHz,
CDCl3): d=172.0 (C=O), 169.4 (C=O), 134.1 (Ar-C), 132.4 (Ar-C), 131.1
(Ar-C), 131.0 (Ar-C), 130.7 (Ar-C), 129.5 (3C; Ar-C), 129.0 (Ar-C), 127.3
(Ar-C), 126.6 (Ar-C), 126.5 (2C; Ar-C), 125.4 (Ar-C), 124.0 (Ar-C), 123.2
3H; Cyclohexyl-H); 13C NMR (75 MHz, CDCl3): d=172.3 (C=O), 169.0
(C=O), 131.0 (Ar-C), 129.4 (2C; Ar-C), 129.3 (Ar-C), 126.4 (2C; Ar-C),
60.1 (OCCH), 56.8 (SO2CH), 28.0 (CH2), 26.8 (CH2), 25.0 (CH2), 24.9
~
(CH2), 24.7 (CH2), 22.6 ppm (CH2); IR (neat): n=2933, 2853, 1967, 1781,
1708, 1598, 1499, 1454, 1391, 1308, 1267, 1184, 1124, 926, 851, 821, 773,
695, 604 cmꢀ1; MS (APCI): m/z (%): 322 (38) [M+H+], 240 (99), 198 (3),
176 (100), 149 (17); HRMS (APCI): m/z calcd for C16H19NO4S+H:
322.1108, found: 322.1102.
~
(Ar-C), 57.6 (SO2C), 55.9 (SO2C), 27.7 ppm (SO2CHCH2); IR (neat): n=
2985, 1966, 1712, 1596, 1498, 1386, 1313, 1192, 1129, 928, 776, 691,
655 cmꢀ1; MS (APCI): m/z (%): 380 (2) [M+H+], 316 (8), 240 (8), 223
(2), 176 (11), 141 (100), 115 (2); HRMS (APCI): m/z calcd for
C21H17NO4S+H: 380.0951, found: 380.0962.
3-(Hex-5-enylsulfonyl)-1-phenylpyrrolidine-2,5-dione (35): The thioether
was prepared according to GPI and obtained after flash column chroma-
tography (petroleum ether/ethyl acetate gradient 10/1!5/1) as a colorless
solid (876 mg, 3.03 mmol, 61% yield). Rf =0.22 (petroleum ether/ethyl
acetate 5/1); m.p.: 42–438C; 1H NMR (300 MHz, CDCl3): d=7.53–7.45
(m, 2H; Ar-H), 7.44–7.37 (m, 1H; Ar-H), 7.33–7.27 (m, 2H; Ar-H), 5.80
(ddt, J=17.2, 10.2, 6.7 Hz, 1H; =CH), 5.06–4.94 (m, 2H; =CH2), 3.87
(dd, J=9.1, 3.4 Hz, 1H; SCH), 3.31 (dd, J=18.9, 9.1 Hz, 1H; SCHCH2),
2.98 (ddd, J=12.5, 8.0, 6.1 Hz, 1H; SCH2), 2.82 (ddd, J=12.5, 7.8, 6.4 Hz,
1H; SCH2), 2.68 (dd, J=18.9, 3.4 Hz, 1H; SCHCH2), 2.09 (q, J=7.0 Hz,
2H; =CHCH2), 1.80–1.60 (m, 2H; SCH2CH2), 1.60–1.45 ppm (m, 2H; =
CHCH2CH2); 13C NMR (75 MHz, CDCl3): d=175.5 (C=O), 173.8 (C=
O), 138.2 (=CH), 131.6 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C), 126.4
(2C; Ar-C), 114.9 (=CH2), 39.0 (SCH), 36.2 (SCHCH2), 33.2 (CH2), 31.7
3-(Hexadecylsulfonyl)-1-phenylpyrrolidine-2,5-dione (33): The thioether
was prepared according to GPII and obtained as a white solid (1.81 g,
4.2 mmol, 84% yield). Rf =0.64 (petroleum ether/ethyl acetate 3/1); m.p.
1
65–678C; H NMR (300 MHz, CDCl3): d=7.53–7.27 (m, 5H; Ar-H), 3.87
(dd, J=9.1, 3.6 Hz, 1H; SCH), 3.31 (dd, J=18.7, 9.1 Hz, 1H; SCHCH2),
3.01–2.90 (m, 1H; SCH2), 2.86–2.75 (m, 1H; SCH2), 2.69 (dd, J=18.7,
3.6 Hz, 1H; SCHCH2), 1.66 (mc, 2H; SCH2CH2), 1.49–1.17 (m, 26H; S-
ACHTUNGTRENNUNG(CH2)2ACHTUNGTRENNUNG
(CH2)13), 0.88 ppm (mc, 3H; CH3); 13C NMR (75 MHz, CDCl3):
d=175.6 (C=O), 173.8 (C=O), 131.7 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-
C), 126.4 (2C; Ar-C), 39.1 (SCH), 36.2 (SCHCH2), 31.9 (2C; CH2), 29.7
(3C; CH2), 29.6 (3C; CH2), 29.6 (CH2), 29.5 (CH2), 29.4 (CH2), 29.2
(CH2), 29.0 (CH2), 28.8 (CH2), 22.7 (CH2), 14.1 ppm (CH3); IR (neat):
~
~
n=2916, 2849, 1782, 1701, 1597, 1502, 1466, 1393, 1174, 1074, 930, 747,
(CH2), 28.4 (CH2), 27.9 ppm (CH2); IR (neat): n=3071, 2941, 2920, 2856,
722, 697, 623, 570 cmꢀ1; MS (EI, 70 eV): m/z (%): 454 (100) [M+Na+];
HRMS (ESI): m/z calcd for C26H41NO2S: 454.2750, found: 454.2753. The
thioether was then oxidized to sulfone 33 according to GPIII. After
column chromatography (petroleum ether/ethyl acetate 2/1) the product
was obtained as a white solid (689 mg, 1.49 mmol, 74% yield). Rf =0.47
(petroleum ether/ethyl acetate 2/1); m.p. 136–1378C; 1H NMR
(300 MHz, CDCl3): d=7.54–7.40 (m, 3H; Ar-H), 7.32–7.27 (m, 2H; Ar-
H), 4.37 (dd, J=9.8, 4.0 Hz, 1H; SO2CH), 3.56–3.43 (m, 3H; SO2CHCH2
and SO2CH2), 3.20 (dd, J=19.2, 9.8 Hz, 1H; SO2CHCH2), 2.02–1.89 (m,
1966, 1780, 1703, 1492, 1455, 1430, 1391, 1299, 1210, 1182, 1157, 992, 905,
790, 751, 697, 629 cmꢀ1; MS (ESI): m/z (%): 312 (100) [M+Na+], 290
(79), 242 (4), 208 (44), 182 (1), 149 (4), 117 (1); HRMS (ESI): m/z calcd
for C16H19NO2S+Na: 312.1029, found: 312.1031. The thioether was then
oxidized to sulfone 35 according to GPIV. After column chromatography
(petroleum ether/ethyl acetate 1/1) the product was obtained as a white
solid (566 mg, 1.76 mmol, 58% yield). Rf =0.52 (petroleum ether/ethyl
acetate 1/1); m.p. 123–1248C; 1H NMR (300 MHz, CDCl3): d=7.54–7.40
(m, 3H; Ar-H), 7.31–7.25 (m, 2H; Ar-H), 5.78 (ddt, J=17.1, 10.3, 6.8 Hz,
1H; =CH), 5.05 (d, J=17.1 Hz, 1H; =CH2), 5.01 (d, J=10.3 Hz, 1H; =
CH2), 4.37 (dd, J=9.7, 4.0 Hz, 1H; SO2CH), 3.55–3.45 (m, 3H; SO2CH2
and SO2CHCH2), 3.20 (dd, J=19.2, 9.7 Hz, 1H; SO2CH2), 2.14 (q, J=
7.2 Hz, 2H; =CHCH2), 2.06–1.91 (m, 2H; SO2CH2CH2), 1.67–1.57 ppm
2H; SO2CH2CH2), 1.55–1.45 (m, 2H; SO
2ACHTUNGTRENNUN(G CH2)2CH2), 1.41–1.21 (m,
24H; SO2A(CH2)3A
C
CHTUNGTRENNUNG
CDCl3): d=172.1 (C=O), 168.9 (C=O), 131.0 (Ar-C), 129.4 (2C; Ar-C),
129.3 (Ar-C), 126.4 (2C; Ar-C), 59.9 (SO2CH), 52.7 (SO2CH2), 31.9
(CH2), 29.7 (2C; CH2), 29.7 (2C; CH2), 29.6 (CH2), 29.6 (CH2), 29.5
(CH2), 29.4 (CH2), 29.2 (CH2), 29.0 (CH2), 28.4 (CH2), 27.9 (CH2), 22.7
(m, 2H; SO2ACTHNUTRGNEUNG
(CH2)2CH2); 13C NMR (75 MHz, CDCl3) d= 172.1 (C=O),
168.9 (C=O), 137.3 (=CH), 130.8 (Ar-C), 129.4 (2C; Ar-C), 129.3 (Ar-C),
126.4 (2C; Ar-C), 115.7 (=CH2), 59.9 (SO2CH), 52.5 (SO2CH2), 33.0 (=
~
(CH2), 21.7 (CH2), 14.1 ppm (CH3); IR (neat) n=2852, 2916, 2850, 1782,
~
1710, 1598, 1500, 1471, 1396, 2390, 1269, 1201, 1185, 1120, 928, 825, 734,
720, 695, 626, 584 cmꢀ1; MS (ESI): m/z (%): 486 (100) [M+Na+], 398
(13), 342 (1), 311 (1); HRMS (ESI): m/z calcd for C26H41NO4S+Na:
486.2649, found: 486.2635.
CHCH2), 27.8 (CH2), 27.5 (CH2), 21.1 ppm (CH2); IR (neat): n=3075,
2971, 2951, 2875, 1966, 1784, 1707, 1639, 1598, 1498, 1456, 1393, 1307,
1270, 1187, 1119, 996, 915, 811, 783, 726, 694 cmꢀ1; MS (APCI): m/z (%):
322 (17) [M+H+], 240 (62), 176 (100), 149 (10), 131 (3); HRMS (APCI):
m/z calcd for C16H19NO4S+H: 322.1108, found: 322.1116.
3-(Cyclohexylsulfonyl)-1-phenylpyrrolidine-2,5-dione (34): The thioether
was prepared according to GPI and obtained after flash column chroma-
tography (petroleum ether/ethyl acetate gradient 5/1!4/1) as a colorless
solid (340 mg, 1.17 mmol, 23% yield). Rf =0.27 (petroleum ether/ethyl
acetate 5/1); m.p. 95–968C; 1H NMR (300 MHz, CDCl3): d=7.52–7.44
(m, 2H; Ar-H), 7.44–7.36 (m, 1H; Ar-H), 7.33–7.27 (m, 2H; Ar-H), 3.97
(dd, J=9.0, 3.7 Hz, 1H; OCCH), 3.31 (dd, J=18.4, 9.0 Hz, 1H; OCCH2),
3.33–3.21 (m, 1H; SCH), 2.69 (dd, J=18.4, 3.7 Hz, 1H; OCCH2), 2.25–
2.13 (m, 1H; Cyclohexyl-H), 2.02–1.90 (m, 1H; Cyclohexyl-H), 1.86–1.73
(m, 2H; Cyclohexyl-H), 1.69–1.59 (m, 1H; Cyclohexyl-H), 1.48–1.19 ppm
(m, 5H; Cyclohexyl-H); 13C NMR (75 MHz, CDCl3): d=175.5 (C=O),
173.9 (C=O), 131.7 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C), 126.4 (2C;
Ar-C), 43.9 (OCCH), 37.7 (SCH), 36.5 (CH2), 33.5 (CH2), 32.9 (CH2),
3-(Cinnamylsulfonyl)-1-phenylpyrrolidine-2,5-dione (36): The thioether
was prepared according to GPI and obtained after flash column chroma-
tography (petroleum ether/ethyl acetate gradient 10/1!5/1) as a white
solid (1.17 g, 3.6 mmol, 72% yield). Rf =0.17 (petroleum ether/ethyl ace-
1
tate 5/1); m.p. 119–1208C; H NMR (300 MHz, CDCl3): d=7.51–7.22 (m,
10H; Ar-H), 6.64 (d, J=15.8 Hz, 1H; PhCH), 6.24 (ddd, J=15.8, 9.4,
6.2 Hz, 1H; PhCHCH), 3.95 (dd, J=14.0, 9.4 Hz, 1H; SCH2), 3.88 (dd,
J=9.4, 3.8 Hz, 1H; SCH), 3.46 (ddd, J=14.0, 6.2, 1.4 Hz, 1H; SCH2),
3.27 (dd, J=18.4, 9.4 Hz, 1H; SCHCH2), 2.69 ppm (dd, J=18.4, 3.8 Hz,
1H; SCHCH2); 13C NMR (75 MHz, CDCl3) d=175.9 (C=O), 173.7 (C=
O), 136.2 (Ar-C), 134.2 (PhCH), 131.6 (Ar-C), 129.2 (2C; Ar-C), 128.8
(PHCHCH), 128.7 (2C; Ar-C), 128.0 (Ar-C), 126.5 (2C; Ar-C), 126.4
(2C; Ar-C), 123.7 (Ar-C), 36.7 (SCH), 35.5 (SCHCH2), 34.5 ppm (SCH2);
~
26.0 (CH2), 25.7 (CH2), 25.6 ppm (CH2); IR (neat): n=2930, 2851, 2555,
~
2185, 2107, 1967, 1703, 1594, 1504, 1455, 1383, 1203, 1164, 1074, 967, 752,
698 cmꢀ1; MS (ESI): m/z (%): 312 (100) [M+Na+], 208 (19); HRMS
(ESI): m/z calcd for C16H19NO2S+Na: 312.1029, found: 312.1023. The
thioether was then oxidized to sulfone 34 according to GPIV. After
column chromatography (petroleum ether/ethyl acetate 2/1) the product
was obtained as a white solid (265 mg, 0.82 mmol, 70% yield). Rf =0.23
(petroleum ether/ethyl acetate 2/1); m.p. 147–1498C; 1H NMR
(300 MHz, CDCl3): d=7.54–7.39 (m, 3H; Ar-H), 7.31–7.25 (m, 2H; Ar-
H), 4.51 (dd, J=9.8, 3.8 Hz, 1H; OCCH), 3.68 (tt, J=12.1, 3.5 Hz, 1H;
SO2CH), 3.51 (dd, J=19.2, 3.8 Hz, 1H; OCCH2), 3.19 (dd, J=19.2,
9.8 Hz, 1H; OCCH2), 2.33–2.22 (m, 2H; Cyclohexyl-H), 2.04–1.91 (m,
2H; Cyclohexyl-H), 1.81–1.57 (m, 3H; Cyclohexyl-H), 1.51–1.19 ppm (m,
IR (neat): n=3057, 3026, 2958, 1782, 1705, 1593, 1490, 1391, 1202, 1188,
1165, 965, 925, 785, 749, 699, 687, 629, 551 cmꢀ1; MS (ESI): m/z (%): 346
(100) [M+Na+], 263 (7), 177 (2), 159 (2), 117 (52), 99 (2); HRMS (ESI):
m/z calcd for C19H17NO2S+Na: 346.0872, found: 346.0889. The thioether
was then oxidized to sulfone 36 according to GPIV. After column chro-
matography (petroleum ether/ethyl acetate 1/1) the product was obtained
as a white solid (362 mg, 1.02 mmol, 68% yield). Rf =0.73 (petroleum
ether/ethyl acetate 1/1); m.p. 160–1618C; 1H NMR (300 MHz, CDCl3):
d=7.57–7.24 (m, 10H; Ar-H), 6.99 (d, J=16.2 Hz, 1H; PhCH), 6.30
(ddd, J=16.2, 9.6, 5.6 Hz, 1H; PhCHCH), 4.67–4.58 (m, 2H; SO2CH and
SO2CH2), 4.13 (ddd, J=14.2, 5.6, 1.5 Hz, 1H; SO2CH2), 3.47 (dd, J=19.3,
4.2 Hz, 1H; SO2CHCH2), 3.15 ppm (dd, J=19.3, 9.6 Hz, 1H;
10424
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 10417 – 10430

a-Sulfonyl Succinimides
FULL PAPER
SO2CHCH2); 13C NMR (75 MHz, CDCl3): d=172.0 (C=O), 169.0 (C=O),
141.0 (PhCH), 135.2 (Ar-C), 131.0 (Ar-C), 129.5 (2C; Ar-C), 129.4 (Ar-
C), 129.1 (Ar-C), 128.4 (2C; Ar-C), 126.9 (2C; Ar-C), 126.4 (2C; Ar-C),
114.1 (PhCHCH), 57.2 (SO2C), 56.6 (SO2C), 27.5 ppm (SO2CHCH2); IR
1190, 1134, 1108, 1032, 926, 787, 746, 692, 586 cmꢀ1; MS (CI): m/z (%):
353 (18) [M+], 338 (2), 326 (5), 312 (4), 298 (100), 280 (11), 254 (1), 202
(1), 188 (2), 174 (18), 146 (1), 119 (2), 91 (1), 65 (1), 57 (9), 43 (1);
HRMS (ESI): m/z calcd for C16H19NO6S+Na: 376.0825, found: 376.0814.
~
(neat): n=2981, 2363, 1966, 1713, 1377, 1257, 1079, 1045, 1009, 913, 862,
3-(Benzyloxymethylsulfonyl)-1-phenylpyrrolidine-2,5-dione (39): The thi-
oether was prepared according to GPI and obtained after flash column
chromatography (petroleum ether/ethyl acetate 4/1) as a light yellow
solid (470 mg, 1.44 mmol, 29% yield). Rf =0.15 (petroleum ether/ethyl
acetate 4/1); m.p. 90–918C; 1H NMR (300 MHz, CDCl3): d=7.48–7.30
(m, 8H; Ar-H), 7.26–7.21 (m, 2H; Ar-H), 5.27 (d, J=12.0 Hz, 1H;
PhCH2), 4.75 (d, J=11.7 Hz, 1H; SCH2), 4.71 (d, J=12.0 Hz, 1H;
PhCH2), 4.61 (d, J=11.7 Hz, 1H; SCH2), 4.08 (dd, J=9.5, 4.2 Hz, 1H;
SCH), 3.36 (dd, J=19.0, 9.5 Hz, 1H; SCHCH2), 2.90 ppm (dd, J=19.0,
4.2 Hz, 1H; SCHCH2); 13C NMR (75 MHz, CDCl3): d=175.5 (C=O),
173.8 (C=O), 136.6 (Ar-C), 131.7 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C),
128.6 (2C; Ar-C), 128.3 (2C; Ar-C), 128.1 (Ar-C), 126.5 (2C; Ar-C), 71.5
647, 605 cmꢀ1; MS (ESI): m/z (%): 378 (100) [M+Na+], 314 (9), 285 (17),
117 (52); HRMS (ESI): m/z calcd for C19H17NO4S+Na: 378.0770, found:
378.0778.
3-(Cyclopropylmethylsulfonyl)-1-phenylpyrrolidine-2,5-dione (37): The
thioether was prepared according to GPI and obtained after column
chromatography (petroleum ether/ethyl acetate 5/1) as a white solid
(685 mg, 2.62 mmol, 53% yield). Rf =0.16 (petroleum ether/ethyl acetate
5/1); m.p. 75–768C; 1H NMR (300 MHz, CDCl3): d=7.53–7.45 (m, 2H;
Ar-H), 7.44–7.36 (m, 1H; Ar-H), 7.33–7.27 (m, 2H; Ar-H), 4.04 (dd, J=
9.0, 3.5 Hz, 1H; SCH), 3.33 (d, J=18.8, 9.0 Hz, 1H; SCHCH2), 2.93 (dd,
J=13.1, 7.5 Hz, 1H; SCH2), 2.74 (dd, J=13.1, 6.7 Hz, 1H; SCH2), 2.70
(dd, J=18.8, 3.5 Hz, 1H; SCHCH2), 1.06 (mc, 1H; SCH2CH), 0.70–0.53
(m, 2H; Cyclopropyl-H), 0.43–0.33 (m, 1H; Cyclopropyl-H), 0.29–
0.18 ppm (m, 1H; Cyclopropyl-H); 13C NMR (75 MHz, CDCl3): d=175.7
(C=O), 173.8 (C=O), 131.6 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C), 126.4
(2C; Ar-C), 38.6 (SC), 37.3 (SC), 36.2 (SCHCH2), 10.6 (SCH2CH), 6.0
~
(PhCH2), 70.5 (SCH2), 38.2 (SCH), 36.2 ppm (SCHCH2); IR (neat): n=
3065, 2949, 2926, 2872, 1966, 1778, 1701, 1594, 1496, 1455, 1388, 1205,
1171, 1055, 1029, 997, 927, 890, 777, 741, 696, 675, 607 cmꢀ1; MS (ESI):
m/z (%): 350 (100) [M+Na+], 328 (6), 298 (19), 251 (2), 220 (5), 91 (5);
HRMS (ESI): m/z calcd for C18H17NO3S+Na: 350.0821, found: 350.0835.
The thioether was then oxidized to sulfone 39 according to GPIII. After
column chromatography (petroleum ether/ethyl acetate 1/1) the product
was obtained as a light yellow solid (282 mg, 0.78 mmol, 54% yield). Rf =
0.67 (petroleum ether/ethyl acetate 1/1); m.p. 117–1188C; 1H NMR
(300 MHz, CDCl3): d=7.53–7.35 (m, 8H; Ar-H), 7.29–7.24 (m, 2H; Ar-
H), 5.33 (d, J=12.5 Hz, 1H; PhCH2), 5.07 (d, J=11.6 Hz, 1H; SO2CH2),
4.89 (d, J=11.6 Hz, 1H; SO2CH2), 4.77 (dd, J=10.2, 5.4 Hz, 1H;
SO2CH), 4.56 (d, J=12.5 Hz, 1H; PhCH2), 3.48 (dd, J=19.3, 4.4 Hz, 1H;
SO2CHCH2), 3.22 ppm (dd, J=19.3, 10.2 Hz, 1H; SO2CHCH2);
13C NMR (125 MHz, CDCl3): d=172.0 (C=O), 168.5 (C=O), 135.3 (Ar-
C), 131.0 (Ar-C), 129.4 (2C; Ar-C), 129.3 (Ar-C), 128.9 (Ar-C), 128.8
(2C; Ar-C), 128.6 (2C; Ar-C), 126.4 (2C; Ar-C), 81.8 (SO2CH2), 75.1
~
(CH2), 4.9 ppm (CH2); IR (neat): n=3051, 3007, 2949, 2915, 1966, 1781,
1701, 1594, 1499, 1488, 1389, 1254, 1206, 1175, 1021, 944, 927, 829, 784,
747, 698, 628, 567 cmꢀ1; MS (ESI): m/z (%): 284 (100) [M+Na+], 266
(2); HRMS (ESI): m/z calcd for C14H15NO2S+Na: 284.0716, found:
284.0714. The thioether was then oxidized to sulfone 37 according to
GPIII. After column chromatography (petroleum ether/ethyl acetate 1/1)
the product was obtained as a white solid (205 mg, 0.7 mmol, 70% yield).
Rf =0.46 (petroleum ether/ethyl acetate 1/1); m.p. 128–1308C; 1H NMR
(300 MHz, CDCl3): d=7.55–7.40 (m, 3H; Ar-H), 7.31–7.27 (m, 2H; Ar-
H), 4.63 (dd, J=9.9, 4.2 Hz, 1H; SO2CH), 3.53 (dd, J=19.1, 4.2 Hz, 1H;
SO2CHCH2), 3.44 (d, 3.7 Hz, 1H; SO2CH2), 3.41 (d, J=5.8 Hz, 1H;
SO2CH2), 3.22 (dd, J=19.1, 9.9 Hz, 1H; SO2CHCH2), 1.38–1.23 (m, 1H;
SO2CH2CH), 0.88–0.75 (m, 2H; Cyclopropyl-H), 0.74–0.64 (m, 1H; Cy-
clopropyl-H), 0.57–0.49 ppm (m, 1H; Cyclopropyl-H); 13C NMR
(75 MHz, CDCl3): d=172.1 (C=O), 169.1 (C=O), 131.0 (Ar-C), 129.4
(2C; Ar-C), 129.3 (Ar-C), 126.4 (2C; Ar-C), 58.9 (SO2C), 57.4 (SO2C),
27.7 (SO2CHCH2), 5.0 (SO2CH2CH), 4.4 (CH2), 4.2 ppm (CH2); IR
~
(PhCH2), 57.1 (SO2CH), 27.5 ppm (SO2CHCH2); IR (neat): n=3064,
2946, 1965, 1783, 1703, 1955, 1499, 1455, 1387, 1304, 1245, 1184, 1173,
1147, 1105, 1077, 1026, 989, 928, 892, 746, 693, 620, 586 cmꢀ1; MS (ESI):
m/z (%): 382 (100) [M+Na+], 343 (11), 318 (14), 266 (34), 251 (14), 186
(1), 149 (2), 91 (9); HRMS (ESI): m/z calcd for C18H17NO5S+Na:
382.0720, found: 382.0714.
~
(neat): n=2922, 2852, 1785, 1713, 1597, 1498, 1458, 1386, 1313, 1189,
1132, 1028, 928, 803, 729, 696, 624 cmꢀ1; MS (ESI): m/z (%): 316 (100)
[M+Na+]; HRMS (ESI): m/z calcd for C14H15NO4S+Na: 316.0614,
found: 316.0592.
1-Phenyl-3-(pyridin-2-ylsulfonyl)pyrrolidine-2,5-dione (49): N-Phenylma-
leimide (868 mg, 5 mmol) was dissolved in acetonitrile (15 mL) and trie-
thylamine (10 drops) was added. After slow addition of a solution of 2-
mercaptopyridine in acetonitrile (20 mL), the reaction mixture was
stirred at room temperature overnight. The solvent was evaporated in
vacuo and the residue purified by flash chromatography on silica gel (pe-
troleum ether/ethyl acetate gradient 2/1!1/2). The thioether[35] was ob-
tained as a white solid (1.07 g, 3.8 mmol, 75% yield). Rf =0.28 (petrole-
um ether/ethyl acetate 2/1); m.p. 145–1468C; 1H NMR (300 MHz,
CDCl3): d=8.31 (mc, 1H; Ar-H), 7.59–7.32 (m, 6H; Ar-H), 7.23 (d, J=
8.0 Hz, 1H; Ar-H), 7.03 (ddd, J=7.6, 4.9, 1.3 Hz, 1H; Ar-H), 4.28 (dd,
J=9.8, 5.5 Hz, 1H; SCH), 3.41 (dd, J=18.5, 9.8 Hz, 1H; SCHCH2),
3.15 ppm (dd, J=18.5, 5.5 Hz, 1H; SCHCH2); 13C NMR (75 MHz,
CDCl3): d=175.1 (C=O), 174.5 (C=O), 155.9 (Ar-C), 149.1 (Ar-C), 136.8
(Ar-C), 132.5 (Ar-C), 129.2 (2C; Ar-C), 128.6 (Ar-C), 126.5 (2C; Ar-C),
122.2 (Ar-C), 120.3 (Ar-C), 41.0 (SCH), 36.6 ppm (SCHCH2); IR (neat):
tert-Butyl 2-(2,5-dioxo-1-phenylpyrrolidin-3-ylsulfonyl)acetate (38): The
thioether was prepared according to GPI and obtained after flash column
chromatography (petroleum ether/ethyl acetate gradient 5/1!4/1) as a
colorless liquid (1.04 g, 3.23 mmol, 65% yield). Rf =0.16 (petroleum
ether/ethyl acetate 4/1); 1H NMR (300 MHz, CDCl3): d=7.53–7.27 (m,
5H; Ar-H), 4.21 (brd, J=6.1 Hz, 1H; SCH), 3.85 (d, J=15.9 Hz, 1H;
SCH2), 3.37 (d, J=15.9 Hz, 1H; SCH2), 3.33 (dd, J=18.7, 8.6 Hz, 1H;
SCHCH2), 2.72 (d, J=18.7 Hz, 1H; SCHCH2), 1.49 ppm (s, 9H; C-
ACHTUNGTRENNUNG
(CH3)3); 13C NMR (75 MHz, CDCl3): d=175.2 (C=O), 173.5 (C=O),
168.7 (CO2), 131.5 (Ar-C), 129.2 (2C; Ar-C), 128.8 (Ar-C), 126.5 (2C;
Ar-C), 82.5 (OC), 38.5 (SC), 35.7 (SC), 34.3 (SCHCH2), 28.0 ppm (3C;
~
CACHTUNGTRENNUNG(CH3)3); IR (neat): n=2979, 2933, 1965, 1782, 1706, 1597, 1500, 1456,
1369, 1300, 1258, 1168, 1125, 952, 851, 744, 694, 619, 572 cmꢀ1; MS (ESI):
m/z (%): 344 (100) [M+Na+], 322 (11), 288 (9), 266 (41), 248 (5), 220
(19), 174 (4); HRMS (ESI): m/z calcd for C16H19NO4S+Na: 344.0927,
found: 344.0940. The thioether was then oxidized to sulfone 38 according
to GPIV. After column chromatography (petroleum ether/ethyl acetate
1/1) the product was obtained as a white solid (892 mg, 2.52 mmol, 78%
yield). Rf =0.63 (petroleum ether/ethyl acetate 1/1); m.p. 153–1558C;
1H NMR (300 MHz, CDCl3): d=7.54–7.41 (m, 3H; Ar-H), 7.31–7.26 (m,
2H; Ar-H), 5.23 (dd, J=9.8, 4.5 Hz, 1H; SO2CH), 4.82 (d, J=15.5 Hz,
1H; SO2CH2), 4.04 (d, J=15.5 Hz, 1H; SO2CH2), 3.49 (dd, J=19.2,
4.5 Hz, 1H; SO2CHCH2), 3.23 (dd, J=19.2, 9.8 Hz, 1H; SO2CHCH2),
~
n =3469, 3049, 2981, 2914 2850, 1964, 1784, 1704 1597, 1578, 1556, 1498,
1453, 1415, 1383, 1281, 1184, 1126, 1078, 944, 753, 720, 696, 628, 547 cmꢀ1
;
MS (EI, 70 eV): m/z (%): 284 (100) [M+], 251 (18), 229 (1), 191 (9), 174
(9), 164 (94), 136 (48), 119 (9), 111 (84), 91 (7), 79 (14), 67 (12), 55 (16).
The obtained thioether (284 mg, 1 mmol) was then dissolved in dichloro-
methane (5 mL) and cooled to 08C. After addition of mCPBA (75%,
483 mg, 2.1 mmol) the mixture was stirred for 15 min at 08C and for 2 h
at room temperature. The reaction mixture was then diluted with di-
chloromethane (2.5 mL), and saturated NaHCO3 solution (5 mL) was
added. After stirring for 20 min the phases were separated and the aque-
ous phase extracted with chloroform. The combined organic phases were
washed with saturated NaHCO3 solution and brine, dried over Na2SO4,
filtered, and concentrated in vacuo. After column chromatography on
silica gel (petroleum ether/ethyl acetate 1/4) the product was obtained as
1.53 ppm (s, 9H; C
169.0 (C=O), 162.1 (CO2), 130.9 (Ar-C), 129.4 (3C; Ar-C), 126.4 (2C;
Ar-C), 85.0 (OC), 59.6 (SO2C), 56.8 (SO2C), 27.9 (3C; (CH3)3),
27.5 ppm (SO2CHCH2); IR (neat): n=2986, 1967, 1721, 1503, 1390, 1326,
ACHTUNGTRENNUNG
(CH3)3); 13C NMR (75 MHz, CDCl3): d=171.9 (C=O),
CACHTUNGTRENNUNG
~
Chem. Eur. J. 2011, 17, 10417 – 10430
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10425

B. Plietker and M. Jegelka
a white solid (186 mg, 0.59 mmol, 59% yield). Rf =0.66 (petroleum ether/
ethyl acetate 1/5); m.p. 150–1528C; H NMR (300 MHz, CDCl3): d=8.79
(m, 5H; Ar-H), 6.18 (dd, J=17.5, 10.8 Hz, 1H; =CH), 5.44 (d, J=
10.8 Hz, 1H; =CH2), 5.41 (d, J=17.5 Hz, 1H; =CH2), 4.16 (s, 2H;
SO2CH2), 1.52 ppm (s, 6H; 2ꢃCH3); 13C NMR (75 MHz, CDCl3): d=
137.5 (=CH), 131.3 (2C; Ar-C), 128.7 (Ar-C), 128.6 (2C; Ar-C), 127.0
(Ar-C), 118.7 (=CH2), 64.8 (SO2C), 52.9 (SO2CH2), 20.5 ppm (2C; 2ꢃ
1
(mc, 1H; Ar-H), 8.12 (d, J=8.0 Hz, 1H; Ar-H), 8.01 (td, J=7.9, 1.7 Hz,
1H; Ar-H), 7.61 (ddd, J=7.6, 4.6, 1.2 Hz, 1H; Ar-H), 7.49–7.36 (m, 3H;
Ar-H), 7.24–7.18 (m, 2H; Ar-H), 5.17 (dd, J=10.0, 4.3 Hz, 1H; SO2CH),
3.64 (dd, J=19.1, 4.3 Hz, 1H; SO2CHCH2), 3.34 ppm (dd, J=19.1,
10.0 Hz, 1H; SO2CHCH2); 13C NMR (75 MHz, CDCl3): d=172.0 (C=O),
167.8 (C=O), 155.4 (Ar-C), 150.5 (Ar-C), 138.5 (Ar-C), 131.0 (Ar-C),
129.3 (2C; Ar-C), 129.2 (Ar-C), 128.2 (Ar-C), 126.3 (2C; Ar-C), 123.6
~
CH3); IR (neat): n=2989, 2940, 1494, 1455, 1410, 1283, 1156, 1136, 1106,
996, 951, 830, 779, 726, 704, 647 cmꢀ1; MS (EI, 70 eV): m/z (%): 160 (6),
117 (1), 104 (3), 91 (68), 77 (2), 69 (100), 65 (21), 53 (9).
1-((2-Methylbut-3-en-2-ylsulfonyl)methyl)naphthalene (41-A): Sulfone 41
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate 4/1) the product was obtained as a colorless oil
(114 mg, 0.42 mmol, 83% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 4/1). Rf =0.22 (petrole-
um ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3): d=8.01 (d, J=
8.1 Hz, 1H; Ar-H), 7.88–7.82 (m, 2H; Ar-H), 7.60–7.41 (m, 4H; Ar-H),
6.30 (dd, J=17.6, 10.8 Hz, 1H; =CH), 5.52 (d, J=10.7 Hz, 1H; =CH2),
5.49 (d, J=17.6 Hz, 1H; =CH2), 4.63 (s, 2H; CH2), 1.61 ppm (s, 6H; 2ꢃ
CH3); 13C NMR (75 MHz, CDCl3): d=137.6 (=CH), 133.9 (Ar-C), 132.8
(Ar-C), 131.1 (Ar-C), 129.7 (Ar-C), 128.7 (Ar-C), 126.7 (Ar-C), 126.0
(Ar-C), 125.2 (Ar-C), 124.1 (Ar-C), 123.2 (Ar-C), 118.9 (=CH2), 64.9
~
(Ar-C), 59.9 (SO2CH), 29.2 ppm (SO2CHCH2); IR (neat): n=3085, 2951,
1787, 1713, 1597, 1581, 1500, 1434, 1390, 1317, 1193, 1167, 1111, 1085,
990, 790, 763, 749, 733, 697, 623, 606, 553 cmꢀ1; MS (EI, 70 eV): m/z (%):
316 (27) [M+], 299 (1), 252 (30), 234 (7), 207 (2), 196 (28), 174 (72), 156
(16), 132 (11), 119 (15), 91 (9), 79 (100), 64 (4), 55 (29); HRMS (ESI): m/
z calcd for C15H12N2O4S+H: 317.0591, found: 317.0597.
General procedure for the preparation of allylic sulfones by Fe-catalyzed
allylic substitution (GPV): A 10 mL-microwave vial was charged with SI-
MES·CCl3 (10.6 mg, 0.025 mmol), evacuated and filled with nitrogen.
Then dry 2-methoxyethanol (0.5 mL) was added and the mixture heated
for 30 min at 808C in a microwave reactor. This solution was then added
via syringe to a 10 mL-Schlenk tube under N2 atmosphere charged with
Bu4N[Fe(CO)3(NO)] (10.3 mg, 0.025 mmol). After closing the tube, the
reaction mixture was heated at 608C for 60 min in an oil bath. After
cooling to room temperature sulfinate precursor (0.5 mmol) and allylic
carbonate (0.5 mmol) were added to the mixture, and the Schlenk tube
closed and heated at 408C in an oil bath. After full conversion the sol-
vent was evaporated and the residue purified by chromatography on
silica gel.
~
(SO2C), 49.2 (SO2CH2), 20.4 ppm (2C; 2ꢃCH3); IR (neat): n=2979,
1509 1412, 1394, 1288, 1214, 1155, 1104, 992, 942, 869, 807, 784, 744, 652,
617 cmꢀ1; MS (ESI): m/z (%): 297 (100) [M+Na+], 229 (5), 207 (12), 165
(6), 141 (25), 115 (2), 102 (2); HRMS (ESI): m/z calcd for C16H18O2S+
Na: 297.0920, found: 297.0905.
1-(2-Methylbut-3-en-2-ylsulfonyl)hexadecane (42-A): Sulfone 42 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 10/1) the product was obtained as a colorless solid
(112 mg, 0.36 mmol, 71% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 10/1). Rf =0.27 (petro-
leum ether/ethyl acetate 10/1); m.p. 52–538C; 1H NMR (300 MHz,
CDCl3): d=6.12 (dd, J=17.8, 11.2 Hz, 1H; =CH), 5.39 (d, J=11.0 Hz,
1H; =CH2), 5.37 (d, J=17.8 Hz, 1H; =CH2), 2.87 (mc, 2H; SO2CH2),
1-(But-3-en-2-ylsulfonyl)benzene (13-A):[36] Sulfone 13 was prepared ac-
cording to GPV. After column chromatography (petroleum ether/ethyl
acetate 5/1) the product was obtained as
a colorless oil (79 mg,
0.41 mmol, 81% yield). Regioisomers were separated by semi-prepara-
tive HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.24 (petroleum
ether/diethyl ether 3/1); 1H NMR (300 MHz, CDCl3): d=7.87–7.82 (m,
2H; Ar-H), 7.69–7.61 (m, 1H; Ar-H), 7.58–7.50 (m, 2H; Ar-H), 5.83
(ddd, J=17.2, 10.3, 7.9 Hz, 1H; =CH), 5.26 (d, J=10.3 Hz, 1H; =CH2),
5.09 (d, J=17.4 Hz, 1H; =CH2), 3.72 (mc, 1H; SO2CH), 1.44 ppm (d, J=
6.9 Hz, 3H; CH3); 13C NMR (125 MHz, CDCl3): d=136.8 (Ar-C), 133.7
(=CH), 131.2 (Ar-C), 129.3 (2C; Ar-C), 128.8 (2C; Ar-C), 121.8 (=CH2),
1.90–1.78 (m, 2H; CH2), 1.50 (s, 6H; CACHTNUTRGNEUGN(CH3)2), 1.45–1.19 (m, 26H; 13x
CH2), 0.88 ppm (mc, 3H; CH3); 13C NMR (75 MHz, CDCl3): d=137.6 (=
CH), 118.4 (=CH2), 63.8 (SO2C), 46.1 (SO2CH2), 31.9 (CH2), 29.7 (3C;
CH2), 29.7 (2C; CH2), 29.6 (CH2), 29.5 (CH2), 29.4 (CH2), 29.3 (CH2),
29.2 (CH2), 28.8 (CH2), 22.7 (CH2), 20.6 (CH2), 20.2 (2C; CACHTUNGTRENNUNG(CH3)2),
~
14.1 ppm (CH3); IR (neat): n=2916, 2848, 2563, 2372, 2169, 1971, 1470,
1276, 1105, 943, 781, 631, 542 cmꢀ1; MS (EI, 70 eV): m/z (%): 359 (<1)
[M+H+], 294 (1), 273 (3), 255 (1), 224 (2), 139 (1), 125 (1), 97 (2), 83 (3),
69 (100), 57 (9), 41 (13); HRMS (EI): m/z calcd for C21H42O2S+H+:
359.2984, found: 359.3007.
~
64.2 (SO2CH), 13.0 ppm (CH3); IR (neat): n=1416, 1305, 1290, 1145,
1085, 1075, 1024, 998, 970, 798, 752, 715 cmꢀ1; MS (EI, 70 eV): m/z (%):
196 (10) [M+], 170 (19), 141 (19), 125 (10), 77 (61), 55 (100).
1-((E)-But-2-enylsulfonyl)benzene (13-B):[37] Rf =0.24 (petroleum ether/
diethyl ether 3/1); 1H NMR (300 MHz, CDCl3): d= 7.90–7.82 (m, 2H;
Ar-H), 7.70–7.50 (m, 3H; Ar-H), 5.58 (dq, J=15.3, 6.0 Hz, 1H; CH3CH),
5.42 (dtq, J=15.3, 7.1, 1.5 Hz, 1H; CH2CH), 3.73 (d, J=7.3 Hz, 2H;
CH2), 1.68 ppm (d, J=6.1 Hz, 3H; CH3); 13C NMR (125 MHz, CDCl3):
d=138.6 (Ar-C), 136.6 (=CH), 133.7 (Ar-C), 128.9 (2C; Ar-C), 128.5
(2-Methylbut-3-en-2-ylsulfonyl)cyclohexane (43-A): Sulfone 43 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 5/1) the product was obtained as a colorless solid
(93 mg, 0.43 mmol, 86% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.35 (petrole-
um ether/ethyl acetate 5/1); m.p. 63–648C; 1H NMR (300 MHz, CDCl3):
d=6.17 (dd, J=17.7, 10.7 Hz, 1H; =CH), 5.34 (d, J=17.7 Hz, 1H; =
CH2), 5.33 (d, J=10.7 Hz, 1H; =CH2), 3.09 (tt, J=11.9, 3.5 Hz, 1H;
SO2CH), 2.16–2.06 (m, 2H; Cyclohexyl-H), 1.93–1.82 (m, 2H; Cyclohex-
yl-H), 1.70–1.54 (m, 3H; Cyclohexyl-H), 1.51 (s, 6H; 2ꢃCH3), 1.35–
1.15 ppm (m, 3H; Cyclohexyl-H); 13C NMR (75 MHz, CDCl3): d=138.2
(=CH), 117.3 (=CH2), 65.2 (SO2C), 57.8 (SO2CH), 26.9 (2C; CH2), 25.5
~
(2C; Ar-C), 117.0 (=CH), 60.2 (CH2), 18.3 ppm (CH3); IR (neat): n=
1667, 1447, 1319, 1298, 1142, 966, 730, 689 cmꢀ1; MS (EI, 70 eV)): m/z
(%): 196 (1) [M+], 142 (3), 131 (1), 126 (13), 117 (4), 97 (1), 92 (2), 77
(21), 71 (1), 65 (1), 55 (100), 51 (26).
1-[(Z)-But-2-enylsulfonyl)benzene (13-C):[37] Rf =0.24 (petroleum ether/
diethyl ether 3/1); 1H NMR (300 MHz, CDCl3): d=7.92–7.86 (m, 2H;
Ar-H), 7.69–7.61 (m, 1H; Ar-H), 7.59–7.50 (m, 2H; Ar-H), 5.89–5.76 (m,
1H; =CH), 5.50–5.37 (m, 1H; =CH), 3.86 (d, J=7.9 Hz, 2H; CH2),
1.35 ppm (d, J=7.2 Hz, 3H; CH3); 13C NMR (125 MHz, CDCl3): d=
138.5 (Ar-C), 134.0 (=CH), 133.6 (Ar-C), 129.1 (2C; Ar-C), 128.5 (2C;
~
(2C; CH2), 25.1 (CH2), 21.0 ppm (2C; 2ꢃCH3); IR (neat): n=2982, 2920,
2857, 1965, 1728, 1448, 1413, 1272, 1265, 1155, 1129, 1101, 999, 939, 892,
849, 817, 789, 738, 655 cmꢀ1; MS (EI, 70 EV): m/z (%): 216 (2) [M+], 149
(1), 109 (2), 96 (9), 83 (34), 69 (100), 55 (22), 41 (26); HRMS (EI): m/z
calcd for C11H20O2S: 216.1184, found: 216.1174.
~
Ar-C), 116.2 (=CH), 54.8 (CH2), 12.7 ppm (CH3); IR (neat): n=1716,
1447, 1377, 1307, 1143, 1085, 925 cmꢀ1; MS (EI, 70 eV): m/z (%): 196 (1)
[M+], 142 (3), 131 (1), 126 (11), 117 (2), 97 (1), 91 (2), 77 (22), 71 (2), 65
(1), 55 (100), 51 (17).
6-(2-Methylbut-3-en-2-ylsulfonyl)hex-1-ene (44-A): Sulfone 44 was pre-
pared according to GPV. After column chromatography (pentane/diethyl
ether 5/3) the product was obtained as a colorless oil (88 mg, 0.41 mmol,
81% yield). Regioisomers were separated by semi-preparative HPLC
(pentane/diethyl ether 5/3). Rf =0.51 (pentane/diethyl ether 5/3);
1H NMR (300 MHz, CDCl3): d=6.11 (dd, J=17.5, 10.9 Hz, 1H; CCH),
5.78 (ddt, J=17.1, 10.2, 6.8 Hz, 1H; CH2CH), 5.39 (d, J=10.9 Hz, 1H;
CCH=CH2), 5.37 (d, J=17.5 Hz, 1H; CCH=CH2), 5.02 (dq, J=17.1,
1-[(2-Methylbut-3-en-2-ylsulfonyl)methyl]benzene (40-A):[38] Sulfone 40
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate 5/1) the product was obtained as colorless oil
(97 mg, 0.44 mmol, 87% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.19 (petrole-
um ether/diethyl ether 3/1); 1H NMR (300 MHz, CDCl3): d=7.42–7.33
10426
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 10417 – 10430

a-Sulfonyl Succinimides
FULL PAPER
1.6 Hz, 1H; CH2CH=CH2), 4.98 (dq, J=6.8, 1.4 Hz, 1H; CH2CH=CH2),
2.88 (mc, 2H; SO2CH2), 2.09 (q, J=7.2 Hz, 2H; CH2), 1.93–1.80 (m, 2H;
CH2), 1.58–1.49 ppm (m, 8H; CH2 and 2ꢃCH3); 13C NMR (75 MHz,
CDCl3): d=137.7 (=CH), 137.5 (=CH), 118.5 (=CH2), 115.3 (=CH2), 63.9
(SO2C), 45.9 (SO2CH2), 33.2 (CHCH2), 28.0 (CH2), 20.2 (CH2), 20.1 ppm
(100) [M+Na+], 266 (65) [M+NH4+], 210 (6), 193 (7), 125 (2); HRMS
(ESI): m/z calcd for C11H20O4S+Na: 271.0975, found: 271.0962.
1-{[(2-Methylbut-3-en-2-ylsulfonyl)methoxy]methyl}benzene (48-A): Sul-
fone 48 was prepared according to GPV. After column chromatography
(petroleum ether/ethyl acetate 5/1) the product was obtained as a color-
less oil (69 mg, 0.27 mmol, 54% yield). Regioisomers were separated by
semi-preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.31
(petroleum ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3): d=
7.42–7.28 (m, 5H; Ar-H), 6.11 (dd, J=17.4, 10.7 Hz, 1H; =CH), 5.41 (d,
J=17.4 Hz, 1H; =CH2), 5.39 (d, J=10.7 Hz, 1H; =CH2), 4.92 (s, 2H;
SO2CH2), 4.59 (s, 2H; PhCH2), 1.57 ppm (s, 6H; 2ꢃCH3); 13C NMR
(75 MHz, CDCl3): d=136.8 (=CH), 136.0 (Ar-C), 128.6 (2C; Ar-C), 128.4
(3C; Ar-C), 119.0 (=CH2), 80.3 (SO2CH2), 74.6 (PhCH2), 64.6 (SO2C),
~
(2C; 2ꢃCH3); IR (neat): n=2979, 2937, 1969, 1640, 1463, 1414, 1312,
1282, 1156, 1106, 998, 913, 800, 755, 720, 634 cmꢀ1; MS (EI, 70 eV): m/z
(%): 216 (<1) [M+], 149 (1), 109 (1), 83 (2), 69 (100), 55 (2), 41 (16);
HRMS (EI): m/z calcd for C11H20O2S: 216.1184, found: 216.1189.
1-((E)-3-(2-Methylbut-3-en-2-ylsulfonyl)prop-1-enyl)benzene (45-A): Sul-
fone 45 was prepared according to GPV. After column chromatography
(petroleum ether/ethyl acetate 4/1) the product was obtained as a color-
less oil (101 mg, 0.41 mmol, 81% yield). Regioisomers were separated by
semi-preparative HPLC (petroleum ether/ethyl acetate 4/1). Rf =0.21
(petroleum ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3): d=
7.42–7.23 (m, 5H; Ar-H), 6.66 (d, J=15.9 Hz, 1H; PhCH), 6.22 (dt, J=
15.9, 7.5 Hz, 1H; CH2CH), 6.16 (dd, J=17.5, 10.7 Hz, 1H; =CH), 5.43 (d,
J=10.7 Hz, 1H; =CH2), 5.40 (d, J=17.5 Hz, 1H; =CH2), 3.85 (dd, J=7.5,
1.2 Hz, 2H; SO2CH2), 1.55 ppm (s, 6H; 2ꢃCH3); 13C NMR (75 MHz,
CDCl3): d=138.7 (=CH), 137.4 (=CH), 135.9 (Ar-C), 128.7 (2C; Ar-C),
128.4 (Ar-C), 126.7 (2C; Ar-C), 118.7 (CH2CH), 114.9 (=CH2), 64.8
~
20.4 ppm (2C; CH3); IR (neat): n=2984, 2938, 1966, 1455, 1415, 1313,
1285, 1157, 1119, 1092, 998, 933, 915, 897, 736, 698, 612, 544 cmꢀ1; MS
(CI): m/z (%): 255 (17) [M+H+], 247 (4), 225 (11), 185 (8), 157 (23), 132
(2), 121 (5), 105 (17), 91 (100), 69 (27), 65 (5), 57 (2); HRMS (ESI): m/z
calcd for C13H18O3S+NH4: 272.1315, found: 272.1304.
2-(But-3-en-2-ylsulfonyl)pyridine (50-A): Sulfone 50 was prepared ac-
cording to GPV. After column chromatography (petroleum ether/ethyl
acetate 1/3) the product was obtained as a light yellow oil (35 mg,
0.18 mmol, 35% yield). Regioisomers could not be separated. Rf =0.48
(petroleum ether/ethyl acetate 1/3); 1H NMR (300 MHz, CDCl3): d=
8.81–8.75 (m, 1H; Ar-H), 8.08–8.03 (m, 1H; Ar-H), 7.99–7.91 (m, 1H;
Ar-H), 7.60–7.52 (m,1H; Ar-H), 5.80 (ddd, J=17.0, 10.2, 8.3 Hz, 1H; =
CH), 5.24 (d, J=10.1 Hz, 1H; =CH2), 5.14 (d, J=17.1 Hz, 1H; =CH2),
4.39–4.27 (m, 1H; SO2CH), 1.51 ppm (d, J=6.8 Hz, 3H; CH3); 13C NMR
(75 MHz, CDCl3): d=156.1 (Ar-C), 150.2 (Ar-C), 137.8 (Ar-C), 130.8 (=
CH), 127.3 (Ar-C), 123.7 (=CH2), 122.5 (Ar-C), 60.5 (SO2CH), 12.3 ppm
~
(SO2C), 51.8 (SO2CH2), 20.5 ppm (2C; CH3); IR (neat): n=2374, 2108,
1965, 1717, 1645, 1600, 1573, 1473, 1455, 1416, 1288, 1220, 1165, 1102,
1010, 905, 798, 726, 693, 649 cmꢀ1
; MS (ESI): m/z (%): 273 (100)
[M+Na+], 205 (10), 141 (2); HRMS (ESI): m/z calcd for C14H18O2S+
Na: 273.0920, found: 273.0919.
1-[(E)-3-(3-Methylbut-2-enylsulfonyl)prop-1-enyl]benzene (45-B):[39] Rf =
0.21 (petroleum ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3):
d=7.44–7.27 (m, 5H; Ar-H), 6.67 (d, J=15.8 Hz, 1H; PhCH), 6.25 (dt,
J=15.8, 7.6 Hz, 1H; PhCHCH), 5.32 (mc, 1H; C=CH), 3.82 (d, J=
7.6 Hz, 2H; PhCHCHCH2), 3.71 (d, J=7.8 Hz, 2H; SO2CH2), 1.84 (s,
3H; CH3), 1.72 ppm (s, 3H; CH3); 13C NMR (75 MHz, CDCl3): d=142.8
(Ar-C), 138.8 (PhCH), 135.6 (=C), 128.8 (2C; Ar-C), 128.7 (Ar-C), 126.7
(2C; Ar-C), 115.4 (=CH), 110.2 (=CH), 56.0 (PhCHCHCH2), 51.9
~
(CH3); IR (neat) n=2934, 1378, 1309, 1161, 1110, 992, 934, 782, 746,
638 cmꢀ1; MS (EI, 70 eV): m/z (%): 197 (5), 182 (2), 132 (75), 130 (3),
118 (100), 106 (7), 93 (8), 79 (51), 55 (58), 51 (17), 39 (8); HRMS
(APCI): m/z calcd for C9H11NO2S+H: 198.0583, found: 198.0577.
(E)-2-(But-2-enylsulfonyl)pyridine (50-B): Rf =0.48 (petroleum ether/
ethyl acetate 1/3); 1H NMR (300 MHz, CDCl3): d=8.77 (d, J=4.4 Hz,
1H; Ar-H), 8.05 (d, J=7.9 Hz, 1H; Ar-H), 7.95 (dt, J=7.5, 1.8 Hz, 1H;
Ar-H), 7.55 (ddd, J=7.6, 5.0, 1.2 Hz, 1H; Ar-H), 5.75–5.60 (m, 1H; =
CH), 5.49–5.35 (m, 1H; =CH), 4.06 (d, J=7.2 Hz, 2H; SO2CH2),
1.65 ppm (d, J=6.5 Hz, 3H; CH3); 13C NMR (75 MHz, CDCl3): d=150.2
(Ar-C), 137.9 (Ar-C), 137.0 (CH3CH), 127.3 (Ar-C), 122.8 (Ar-C), 116.3
(CH2CH), 55.8 (SO2CH2), 18.2 ppm (CH3); IR (neat): n=3035, 2919,
1452, 1314, 1152, 968 cmꢀ1; MS (EI, 70 eV): m/z (%): 197 (5), 182 (2),
132 (75), 130 (3), 118 (100), 106 (7), 93 (8), 79 (51), 55 (58), 51 (17), 39
(8); HRMS (APCI): m/z calcd for C9H11NO2S+H: 198.0583, found:
198.0577.
1-((But-3-en-2-ylsulfonyl)methyl)benzene (51-A):[38] Sulfone 51 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 5/1) the product was obtained as colorless oil (90 mg,
0.43 mmol, 86% yield). Regioisomers were separated by semi-prepara-
tive HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.33 (petroleum
ether/ethyl acetate 3/1); 1H NMR (300 MHz, CDCl3): d=7.44–7.36 (m,
5H; Ar-H), 5.98 (ddd, J=17.2, 10.4, 8.6 Hz, 1H; =CH), 5.48 (d, J=
10.4 Hz, 1H; =CH2), 5.39 (d, J=17.2 Hz, 1H; =CH2), 4.26 (d, J=13.9 Hz,
1H; SO2CH2), 4.19 (d, J=13.9 Hz, 1H; SO2CH2), 3.65–3.52 (m, 1H;
SO2CH), 1.47 ppm (d, J=7.0 Hz, 3H; CH3); 13C NMR (75 MHz, CDCl3):
d=132.3 (=CH), 130.9 (2C; Ar-C), 129.0 (Ar-C), 128.9 (2C; Ar-C), 127.6
(Ar-C), 122.0 (=CH2), 60.3 (SO2CH), 56.0 (SO2CH2), 12.3 ppm (CH3); IR
~
(SO2CH2), 26.1 (CH3), 18.7 ppm (CH3); IR (neat): n=3050, 2980, 2911,
1671, 1598, 1578, 1494, 1448, 1416, 1374, 1290, 1280, 1225, 1152, 1111,
1057, 976, 914, 847, 754, 732, 720, 695, 593, 565, 539 cmꢀ1; MS (EI,
70 eV): m/z (%): 250 (<1) [M+], 186 (1), 117 (100), 102 (1), 91 (13), 77
(2), 69 (18), 63 (3), 51 (3).
[(2-Methylbut-3-en-2-ylsulfonyl)methyl]cyclopropane (46-A): Sulfone 46
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate 5/1) the product was obtained as a colorless oil
(79 mg, 0.42 mmol, 84% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.26 (petrole-
um ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3): d=6.12 (dd,
J=17.4, 10.6 Hz, 1H; =CH), 5.38 (d, J=10.6 Hz, 1H; =CH2), 5.36 (d, J=
17.4 Hz, 1H; =CH2), 2.85 (d, J=7.1 Hz, 2H; SO2CH), 1.51 (s, 6H; 2ꢃ
CH3), 1.25–1.11 (m, 1H; SO2CH2CH), 0.77–0.68 (m, 2H; CH2), 0.42–
0.35 ppm (m, 2H; CH2); 13C NMR (75 MHz, CDCl3): d=137.6 (=CH),
118.3 (=CH2), 63.8 (SO2C), 51.8 (SO2CH2), 20.2 (2C; CH3), 4.7 (2C;
~
CH2), 3.3 ppm (CH); IR (neat): n=3088, 2984, 2936, 1966, 1464, 1415,
1289, 1258, 1155, 1105, 1024, 1004, 917, 829, 803, 731, 632 cmꢀ1; MS
(ESI): m/z (%): 211 (100) [M+Na+], 206 (1), 143 (5), 102 (3); HRMS
(ESI): m/z calcd for C9H16O2S+Na: 211.0763, found: 211.0761.
tert-Butyl 2-(2-methylbut-3-en-2-ylsulfonyl)acetate (47-A): Sulfone 47
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate 5/1) the product was obtained as a colorless solid
(67 mg, 0.27 mmol, 54% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.24 (petrole-
um ether/ethyl acetate 5/1); m.p. 37–388C; 1H NMR (300 MHz, CDCl3):
d=6.13 (dd, J=17.4, 10.8 Hz, 1H; =CH), 5.45 (d, J=10.8 Hz, 1H; =
CH2), 5.43 (d, J=17.4 Hz, 1H; =CH2), 3.83 (s, 2H; SO2CH2), 1.54 (s, 6H;
~
(neat): n=2987, 2939, 1495, 1455, 1415, 1307, 1116, 1030, 995, 935, 873,
773, 697, 650 cmꢀ1; MS (EI, 70 eV): m/z (%): 210 (<1) [M+], 146 (3),
131 (3), 117 (1), 104 (2), 91 (100), 65 (12), 55 (11).
1-{[(E)-But-2-enylsulfonyl)methyl}benzene (51-B):[40] Rf =0.20 (petrole-
1
um ether/ethyl acetate 5/1); H NMR (300 MHz, CDCl3): d=7.40 (s, 5H;
Ar-H), 5.84 (dqt, J=15.2, 6.7, 1.1 Hz, 1H; CH3CH), 5.55 (dtq, J=15.2,
7.5, 1.5 Hz, 1H; CH2CH), 4.20 (s, 2H; PhCH2), 3.52 (d, J=7.5 Hz, 2H;
SO2CH2), 1.81 ppm (d, J=6.7 Hz, 3H; CH3); 13C NMR (75 MHz,
CDCl3): d=136.6 (CH3CH), 130.7 (2C; Ar-C)), 129.0 (3C; Ar-C), 127.9
(Ar-C), 117.2 (CH2CH), 57.8 (SO2CH2), 55.3 (SO2CH2), 18.3 ppm (CH3);
2ꢃCH3), 1.50 ppm (s, 9H; C
161.5 (C=O), 136.8 (=CH), 120.0 (=CH), 83.7 (OC), 66.1 (SO2C), 53.7
(CH3)3); 13C NMR (75 MHz, CDCl3): d=
ACHTUNGTRENNUNG
~
(SO2CH2), 27.8 (3C; CACHTUNGTRENNUNG(CH3)3), 20.1 ppm (2C; CAHCUTNGERN(NUG CH3)2); IR (neat): n=
2981, 2938, 1967, 1730, 1463, 1395, 1369, 1314, 1288, 1260, 1156, 1108,
1002, 937, 902, 833, 799, 715, 678, 619 cmꢀ1; MS (ESI): m/z (%): 271
IR (neat): n=3034, 2971, 2818, 1856, 1967, 1496, 1455, 1405, 1296, 1259,
~
Chem. Eur. J. 2011, 17, 10417 – 10430
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10427

B. Plietker and M. Jegelka
1237, 1115, 1091, 966, 930, 870, 786, 769, 697, 593 cmꢀ1; MS (EI, 70 eV):
m/z (%): 210 (<1) [M+], 146 (4), 131 (3), 117 (1), 104 (2), 91 (100), 65
(19), 55 (15).
J=15.7 Hz, 1H; CH2CHCH), 4.25 (s, 2H; PhCH2), 3.78 (s, 3H; CH3),
3.70 ppm (d, J=7.7 Hz, 2H; SO2CH2); 13C NMR (75 MHz, CDCl3): d=
165.2 (C=O), 133.1 (CH2CH), 130.7 (2C; Ar-C), 129.4 (Ar-C), 129.2 (2C;
Ar-C), 129.1 (CH2CHCH), 127.3 (Ar-C), 59.2 (SO2CH2), 54.1 (SO2CH2),
1-[(Hept-1-en-3-ylsulfonyl)methyl]benzene (52-A): Sulfone 52 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 5/1) the product was obtained as a colorless oil
(102 mg, 0.41 mmol, 81% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.37 (petrole-
um ether/ethyl acetate 5/1); 1H NMR (300 MHz, CDCl3): d=7.44–7.33
(m, 5H; Ar-H), 5.84 (dt, J=17.1, 10.1 Hz, 1H; =CH), 5.54 (d, J=
10.1 Hz, 1H; =CH2), 5.36 (d, J=17.1 Hz, 1H; =CH2), 4.27 (d, J=13.9 Hz,
1H; SO2CH2), 4.17 (d, J=13.9 Hz, 1H; SO2CH2), 3.37 (ddd, J=11.0,
10.0, 3.3 Hz, 1H; SO2CH), 2.11–1.98 (m, 1H; SO2CHCH2), 1.76–1.60 (m,
1H; SO2CHCH2), 1.44–1.07 (m, 4H; 2ꢃCH2), 0.87 ppm (t, J=7.1 Hz,
3H; CH3); 13C NMR (75 MHz, CDCl3): d=131.6 (=CH), 131.0 (2C; Ar-
C), 128.9 (2C; Ar-C), 128.8 (Ar-C), 127.6 (Ar-C), 123.6 (=CH2), 65.7
(SO2CH), 56.4 (SO2CH2), 28.5 (CHCH2), 25.1 (CH2), 22.2 (CH2),
~
52.0 ppm (CH3); IR (neat): n=3035, 2988, 2955, 2941, 1962, 1718, 1653,
1493, 1441, 1323, 1304, 1283, 1206, 1189, 1144, 1118, 1052, 1027, 1003,
979, 926, 829, 780, 726, 699 cmꢀ1; MS (ESI): m/z (%): 277 (100) [M+Na+
], 223 (3), 122 (1), 91 (7); HRMS (ESI): m/z calcd for C12H14O4S+Na:
277.0505, found: 277.0497.
1-[(4-Methylpent-1-en-3-ylsulfonyl)methyl]benzene (55-A): Sulfone 55
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate 4/1) the product was obtained as a colorless oil
(36 mg, 0.15 mmol, 30% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 4/1). Rf =0.40 (petrole-
1
um ether/ethyl acetate 4/1); H NMR (300 MHz, CDCl3): d=7.38 (s, 5H;
Ar-H), 6.02 (dt, J=17.2, 10.2 Hz, 1H; =CH), 5.60 (dd, J=10.2, 1.5 Hz,
1H; =CH2), 5.33 (dd, J=17.2, 1.3 Hz, 1H; =CH2), 4.26 (d, J=14.0 Hz,
1H; SO2CH2), 4.13 (d, J=14.0 Hz, 1H; SO2CH2), 3.25 (dd, J=10.2,
3.4 Hz, 1H; SO2CH), 2.68–2.51 (m, 1H; CH), 1.08 (d, J=7.0 Hz, 3H;
CH3), 0.93 ppm (d, J=7.0 Hz, 3H; CH3); 13C NMR (75 MHz, CDCl3):
d=130.9 (2C; Ar-C), 129.0 (=CH), 128.9 (2C; Ar-C), 128.8 (Ar-C), 127.9
(Ar-C), 124.4 (=CH2), 69.9 (SO2CH), 57.5 (SO2CH2), 26.1 (CH), 21.6
~
13.8 ppm (CH3); IR (neat): n=2957, 2931, 2871, 1965, 1495, 1456, 1303,
1117, 995, 935, 919, 768, 730, 696, 648, 548 cmꢀ1; MS (ESI): m/z (%): 275
(100) [M+Na+], 157 (22), 91 (2); HRMS (ESI): m/z calcd for
C14H20O2S+Na: 275.1076, found: 275.1085.
1-{[(E)-Hept-2-enylsulfonyl]methyl}benzene (52-B): Rf =0.29 (petroleum
1
~
(CH3), 18.0 ppm (CH3); IR (neat): n=2965, 2367, 2001, 1968, 1457, 1312,
ether/ethyl acetate 5/1); H NMR (300 MHz, CDCl3): d=7.40 (s, 5H; Ar-
1127, 782, 696, 642 cmꢀ1; MS (EI, 70 eV): m/z (%): 238 (<1) [M+], 174
(5), 133 (5), 118 (3), 104 (9), 91 (100), 83 (36), 65 (8), 55 (32), 41 (8);
HRMS (ESI): m/z calcd for C13H18O2S+Na: 261.0920, found: 261.0902.
H), 5.81 (dt, J=15.4, 6.8 Hz, 1H; CH2CH), 5.53 (dtt, J=15.4, 7.2, 1.5 Hz,
1H; SO2CH2CH), 4.20 (s, 2H; PhCH2), 3.53 (d, J=7.2 Hz, 2H; SO2CH2),
2.14 (dt, J=6.8, 6.6 Hz, 2H; CHCH2), 1.48–1.26 (m, 4H; 2ꢃCH2),
0.91 ppm (t, J=7.0 Hz, 3H; CH3); 13C NMR (75 MHz, CDCl3): d=141.9
(CH2CH), 130.8 (2C; Ar-C), 129.0 (2C; Ar-C), 128.9 (Ar-C), 127.9 (Ar-
C), 116.0 (SO2CH2CH), 57.7 (SO2CH2), 55.3 (SO2CH2), 32.4 (CHCH2),
1-{[(E)-4-Methylpent-2-enylsulfonyl]methyl}benzene (55-B): Rf =0.40
(petroleum ether/ethyl acetate 4/1); m.p. 75–768C; 1H NMR (300 MHz,
CDCl3): d=7.40 (s, 5H; Ar-H), 5.77 (dd, J=15.5, 6.7 Hz, 1H;
CH2CHCH), 5.49 (ddt, J=15.5, 7.3, 1.4 Hz, 1H; CH2CH), 4.19 (s, 2H;
PhCH2), 3.52 (d, J=7.3 Hz, 2H; SO2CH2), 2.40 (mc, 1H; CH), 1.05 ppm
(d, J=6.8 Hz, 6H; 2ꢃCH3); 13C NMR (75 MHz, CDCl3): d=148.5
(CH2CHCH), 130.8 (2C; Ar-C), 129.0 (3C; Ar-C), 127.9 (Ar-C), 113.5
(CH2CH), 57.6 (SO2CH2), 55.4 (SO2CH2), 31.4 (CH), 21.9 ppm (2C;
~
30.9 (CH2), 22.2 (CH2), 13.9 ppm (CH3); IR (neat): n=2957, 2927, 2858,
1966, 1496, 1456, 1302, 1259, 1117, 1073, 971, 923, 873, 786, 768, 697,
594 cmꢀ1; MS (ESI): m/z (%): 275 (100) [M+Na+], 157 (14), 91 (1);
HRMS (ESI): m/z calcd for C14H20O2S+Na: 275.1076, found: 275.1085.
1-[1-(Benzylsulfonyl)allyl]benzene (53-A):[38] Sulfone 53 was prepared ac-
cording to GPV. After column chromatography (petroleum ether/ethyl
acetate 4/1) the product was obtained as a white solid (31 mg, 0.12 mmol,
23% yield). Regioisomers were separated by semi-preparative HPLC
(petroleum ether/ethyl acetate 4/1). Rf =0.27 (petroleum ether/ethyl ace-
tate 4/1); m.p. 77–798C; 1H NMR (300 MHz, CDCl3): d=7.45–7.30 (m,
10H; Ar-H), 6.35 (ddd, J=17.0, 10.1, 9.1 Hz, 1H; =CH), 5.56 (d, J=
10.1 Hz, 1H; =CH2), 5.42 (d, J=17.0 Hz, 1H; =CH2), 4.61 (d, J=9.1 Hz,
1H; SO2CH), 4.19 (d, J=14.2 Hz, 1H; SO2CH2), 4.11 ppm (d, J=
14.2 Hz, 1H; SO2CH2); 13C NMR (75 MHz, CDCl3): d=131.6 (Ar-C),
131.0 (2C; Ar-C), 129.9 (=CH), 129.7 (2C; Ar-C), 129.2 (Ar-C), 129.0
(2C; Ar-C), 128.9 (Ar-C), 128.9 (2C; Ar-C), 127.5 (Ar-C), 123.6 (Ar-C),
~
CH3); IR (neat): n=2967, 2956, 2926, 2895, 2868, 1966, 1497, 1456, 1407,
1306, 1261, 1250, 1148, 1116, 967, 878, 786, 728, 698, 595, 562 cmꢀ1; MS
(EI, 70 eV): m/z (%): 238 (<1) [M+], 174 (5), 133 (5), 118 (4), 104 (9),
91 (100), 83 (45), 65 (7), 55 (34), 41 (8); HRMS (ESI): m/z calcd for
C13H18O2S+Na: 261.0920, found: 261.0903.
1-{[2-(Benzylsulfonyl)but-3-enyloxy]methyl}benzene (56-A): Sulfone 56
was prepared according to GPV. After column chromatography (petrole-
um ether/ethyl acetate gradient 3/1!1/1) the product was obtained as a
colorless oil (78 mg, 0.31 mmol, 62% yield). Rf =0.42 (petroleum ether/
ethyl acetate 3/1); 1H NMR (300 MHz, CDCl3): d=7.43–7.26 (m, 10H;
Ar-H), 5.91 (ddd, J=17.2, 10.4, 8.5 Hz. 1H; =CH), 5.52 (d, J=10.4 Hz,
1H; =CH2), 5.44 (d, J=17.2 Hz, 1H; =CH2), 4.59 (s, 2H; PhCH2), 4.40
(d, J=13.6 Hz, 1H; SO2CH2), 4.29 (d, J=13.6 Hz, 1H; SO2CH2), 4.01
(dd, J=9.8, 6.3 Hz, 1H; CHCH2), 3.91 (dd, J=9.8, 4.9 Hz, 1H; CHCH2),
3.81–3.72 ppm (m, 1H; SO2CH); 13C NMR (75 MHz, CDCl3): d=137.1
(=CH), 131.2 (2C; Ar-C), 128.8 (Ar-C), 128.8 (2C; Ar-C), 128.6 (2C; Ar-
C), 128.1 (Ar-C), 128.0 (Ar-C), 127.5 (2C; Ar-C), 127.2 (Ar-C), 124.4 (=
CH2), 73.9 (PhCH2), 67.8 (OCH2), 65.1 (SO2CH), 59.2 ppm (SO2CH2);
~
71.0 (SO2CH), 56.8 ppm (SO2CH2); IR (neat): n=3060, 3033, 2982, 2943,
1959, 1492, 1455, 1416, 1310, 1282, 1218, 1120, 1071, 985, 959, 936, 769,
712, 695, 650, 638, 559 cmꢀ1; MS (EI, 70 eV): m/z (%): 208 (9), 117 (100),
91 (53), 77 (6), 65 (18), 51 (10).
1-[(E)-3-(Benzylsulfonyl)prop-1-enyl]benzene (53-B):[41] Rf =0.21 (petro-
leum ether/ethyl acetate 4/1); m.p. 122–1238C; 1H NMR (300 MHz,
CDCl3): d=7.46–7.27 (m, 10H; Ar-H), 6.63 (d, J=15.9 Hz, 1H; PhCH),
6.22 (dt, J=15.9, 7.6 Hz, 1H; CH2CH), 4.25 (s, 2H; PhCH2), 3.74 ppm (d,
J=7.6 Hz, 1H; SO2CH2); 13C NMR (75 MHz, CDCl3): d=139.2 (PhCH),
135.5 (Ar-C), 130.8 (2C; Ar-C), 129.1 (Ar-C), 129.0 (2C; Ar-C), 128.8
(2C; Ar-C), 128.7 (Ar-C), 127.8 (Ar-C), 126.7 (2C; Ar-C), 115.2
~
IR (neat): n=3032, 2921, 2886, 1966, 1715, 1495, 1455, 1363, 1309, 1257,
1023, 1116, 1028, 991, 937, 739, 696, 648 cmꢀ1; MS (ESI): m/z (%): 339
(100) [M+Na+], 317 (7), 181 (8), 91 (2); HRMS (ESI): m/z calcd for
C18H20O3S+Na: 339.1025, found: 339.1013.
~
(CH2CH), 58.2 (SO2CH2), 55.8 ppm (SO2CH2); IR (neat): n=3059, 3030,
1-{[(E)-4-(Benzylsulfonyl)but-2-enyloxy]methyl}benzene (56-B): Rf =0.16
(petroleum ether/ethyl acetate 3/1); m.p. 68–698C; 1H NMR (300 MHz,
CDCl3): d=7.40 (s, 5H; Ar-H), 7.40–7.27 (m, 5H; Ar-H), 5.95 (dt, J=
15.7, 5.1 Hz, 1H; OCH2CH), 5.83 (dt, J=15.7, 7.0 Hz, 1H; SO2CH2CH),
4.54 (s, 2H; PhCH2), 4.21 (s, 2H; SO2CH2), 4.08 (d, J=5.1 Hz, 2H;
OCH2), 3.59 ppm (d, J=7.0 Hz, 2H; CHCH2); 13C NMR (75 MHz,
CDCl3): d=137.8 (Ar-C), 137.2 (OCH2CH), 130.8 (2C; Ar-C), 129.1 (Ar-
C), 129.0 (2C; Ar-C), 128.5 (2C; Ar-C), 127.9 (Ar-C), 127.8 (2C; Ar-C),
127.7 (Ar-C), 118.6 (SO2CH2CH), 72.6 (PhCH2), 69.6 (OCH2), 58.3
2981, 2936, 1965, 1716, 1491, 1449, 1410, 1279, 1162, 1115, 1074, 1055,
1026, 974, 912, 824, 776, 749, 726, 696, 603, 546 cmꢀ1; MS (EI, 70 eV): m/
z (%): 272 (<1) [M+], 208 (4), 117 (100), 102 (1), 91 (38), 77 (2), 65 (13),
51 (4).
(E)-Methyl-4-(benzylsulfonyl)but-2-enoate (54-B): Sulfone 54 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 2/1) the product was obtained as a white solid (53 mg,
0.21 mmol, 42% yield). Regioisomers were separated by semipreparative
HPLC (petroleum ether/ethyl acetate 2/1). Rf =0.21 (petroleum ether/
ethyl acetate 2/1); m.p. 102–1048C; 1H NMR (300 MHz, CDCl3): d=
7.45–7.37 (m, 5H; Ar-H), 6.87 (dt, J=15.7, 7.7 Hz, 1H; CH2CH), 6.07 (d,
~
(SO2CH2), 54.8 ppm (SO2CH2); IR (neat): n=3033, 2938, 2861, 2843,
1957, 1726, 1494, 1453, 1410, 1360, 1301, 1280, 1220, 1166, 1119, 1111,
1067, 1026, 1008, 963, 773, 749, 726, 695, 605, 550 cmꢀ1; MS (ESI): m/z
10428
www.chemeurj.org
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2011, 17, 10417 – 10430

a-Sulfonyl Succinimides
FULL PAPER
(%): 339 (100) [M+Na+], 233 (1), 181 (2), 143 (1), 91 (3); HRMS (ESI):
m/z calcd for C18H20O3S+Na: 339.1025, found: 339.1029.
oil (123 mg, 0.44 mmol, 88% yield). Regioisomers were separated by
semi-preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.47
(petroleum ether/ethyl acetate 5/1); ½aꢁ2D0 =ꢀ10 (c=1.0 in diethyl ether);
1H NMR (300 MHz, CDCl3): d=7.84–7.78 (m, 2H; Ar-H), 7.66–7.59 (m,
1H; Ar-H), 7.55–7.47 (m, 2H; Ar-H), 5.92 (dd, J=17.4, 10.7 Hz, 1H; =
CH), 5.37 (d, J=10.8 Hz, 1H; =CH2), 5.06 (d, J=17.4 Hz, 1H; =CH2),
5.09–5.01 (m, 1H; =CH), 1.96–1.84 (m, 4H; 2ꢃCH2), 1.67 (s, 3H; CH3),
1.56 (d, J=0.8 Hz, 3H; CH3), 1.37 ppm (s, 3H; CH3); 13C NMR (75 MHz,
CDCl3): d=135.3 (Ar-C), 135.2 (CH2=CH), 133.5 (Ar-C), 132.6 (=C),
130.8 (2C; Ar-C), 128.3 (2C; Ar-C), 123.0 (C=CH), 120.6 (=CH2), 68.3
(SO2C), 32.7 (CCH2), 25.6 (CH3), 22.5 (CH2), 17.7 (CH3), 16.2 ppm
1-[(E)-3-(Benzylsulfonyl)but-1-enyl]benzene (57-A): Sulfone 57 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 4/1) the product was obtained as
a white solid
(119 mg, 0.42 mmol, 83% yield). Regioisomers were separated by semi-
preparative HPLC (petroleum ether/ethyl acetate 4/1). Rf =0.25 (petrole-
um ether/ethyl acetate 4/1); m.p. 126–1288C; 1H NMR (300 MHz,
CDCl3): d=7.45–7.28 (m, 10H; Ar-H), 6.60 (d, J=15.9 Hz, 1H; PhCH),
6.24 (dd, J=15.9, 9.1 Hz, 1H; PhCHCH), 4.29 (d, J=14.0 Hz, 1H;
SO2CH2), 4.21 (d, J=14.0 Hz, 1H; SO2CH2), 3.73 (dq, J=9.1, 6.8 Hz,
1H; OCH), 1.55 ppm (d, J=6.8 Hz, 3H; CH3); 13C NMR (75 MHz,
CDCl3): d=136.6 (PhCH), 135.5 (Ar-C), 130.9 (2C; Ar-C), 128.9 (3C;
Ar-C), 128.8 (2C; Ar-C), 128.7 (Ar-C), 127.6 (Ar-C), 126.7 (2C; Ar-C),
122.8 (PhCHCH), 60.4 (SO2CH), 56.4 (SO2CH2), 12.8 ppm (CH3); IR
~
(CH3); IR (neat): n=2970, 2917, 1446, 1413, 1376, 1293, 1143, 1068, 999,
929, 758, 724, 689, 622 cmꢀ1; MS (EI, 70 EV): m/z (%): 137 (17), 121 (9),
107 (3), 93 (34), 81 (42), 69 (100), 53 (12) ; HPLC analysis: DAICEL
CHIRALCEL OJ, heptane/isopropyl alcohol 95/5, flow rate:
1.0 mLminꢀ1, detector: 220 nm, tR(R)=12.8 min, tR(S)=16.1 min.
~
(neat): n=3029, 2981, 2937, 1493, 1453, 1312, 1282, 1261, 1211, 1121,
1071, 1020, 969, 774, 758, 725, 700, 623, 588 cmꢀ1; MS (ESI): m/z (%):
309 (70) [M+Na+], 279 (6), 179 (25), 131 (100), 98 (4); HRMS (ESI): m/
z calcd for C17H18O2S+Na: 309.0920, found: 309.0915.
{[(E)-1-Phenylbut-2-enylsulfonyl]methyl}benzene (57-B): Rf =0.43 (pe-
troleum ether/ethyl acetate 4/1); m.p. 106–1078C (decomp.); 1H NMR
(300 MHz, CDCl3): d=7.44–7.29 (m, 10H; Ar-H), 6.05–5.90 (m, 1H;
PhCHCH), 5.84 (dq, J=15.2, 6.0 Hz, 1H; CH3CH), 4.56 (d, J=8.8 Hz,
1H; SO2CH), 4.17 (d, J=14.1 Hz, 1H; SO2CH2), 4.10 (d, J=14.1 Hz,
1H; SO2CH2), 1.81 ppm (dd, J=6.0, 1.0 Hz, 3H; CH3); 13C NMR
(75 MHz, CDCl3): d=135.3 (CH3CH), 132.4 (Ar-C), 130.9 (2C; Ar-C),
129.6 (2C; Ar-C), 129.0 (3C; Ar-C), 128.9 (Ar-C), 128.8 (2C; Ar-C),
127.7 (Ar-C), 122.5 (Ar-C), 70.5 (PhCH), 56.8 (PhCH2), 18.4 ppm (CH3);
Acknowledgements
Financial support by the Fonds der Chemischen Industrie (Ph.D.-grant
for M. J.), the Deutsche Forschungsgemeinschaft, and the Dr-Otto-
Rçhm-Gedꢀchtnisstiftung is gratefully acknowledged.
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York, 1988; c) A.-N. R. Alba, X. Companyo, R. Rios, Chem. Soc.
Rev. 2010, 39, 2018–2033.
~
IR (neat): n=3063, 3033, 2980, 2936, 2916, 1494, 1455, 1316, 1287, 1123,
1074, 966, 802, 764, 711, 697, 637, 593, 525 cmꢀ1; MS (ESI): m/z (%): 309
(67) [M+Na+], 304 (98) [M+NH4+], 279 (4), 179 (15), 131 (100), 91 (2);
HRMS (ESI): m/z calcd for C17H18O2S+Na: 309.0920, found: 309.0915.
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(Z)-tert-Butyl-2-[(benzylsulfonyl)methyl]-3-phenylacrylate 58B: Sulfone
58 was prepared according to GPV. After column chromatography (pe-
troleum ether/ethyl acetate 5/1) the product was obtained as a white
solid (97 mg, 0.26 mmol, 52% yield). Regioisomers were separated by
semi-preparative HPLC (petroleum ether/ethyl acetate 5/1). Rf =0.23
(petroleum ether/ethyl acetate 5/1); m.p. 114–1158C; 1H NMR
(300 MHz, CDCl3): d=8.00 (s, 1H; CH), 7.53–7.31 (m, 10H; Ar-H), 4.33
(s, 2H; SO2CH2), 4.19 (s, 2H; SO2CH2), 1.58 ppm (s, 9H; 3x CH3);
13C NMR (75 MHz, CDCl3): d=166.0 (C=O), 145.6 (PhCH), 134.1 (Ar-
C), 131.1 (2C; Ar-C), 129.5 (Ar-C), 129.3 (2C; Ar-C), 129.0 (Ar-C), 128.9
(2C; Ar-C), 128.8 (2C; Ar-C), 127.9 (Ar-C), 122.7 (=C), 82.3 (OC), 60.8
~
(PhCH2), 51.3 (SO2CH2), 28.1 ppm (3C; CH3); IR (neat): n=3052, 3977,
2929, 1964, 1702, 1622, 1496, 1447, 1367, 1320, 1279, 1245, 1204, 1163,
1148, 1975, 889, 853, 779, 765, 754, 697, 681, 591, 569, 526 cmꢀ1; MS
(ESI): m/z (%): 390 (100) [M+NH4+], 373 (13) [M+H+], 339 (11), 317
(76), 299 (23), 167 (3), 91 (3); HRMS (ESI): m/z calcd for C21H24O4S+
NH4: 390.1734, found: 390.1749.
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1-{[(E)-Pent-3-en-2-ylsulfonyl]methyl}benzene (59): Sulfone 59 was pre-
pared according to GPV. After column chromatography (petroleum
ether/ethyl acetate 5/1) the product was obtained as colorless oil (98 mg,
0.44 mmol, 88% yield). Rf =0.19 (petroleum ether/ethyl acetate 5/1) ;
1H NMR (300 MHz, CDCl3): d=7.44–7.34 (m, 5H; Ar-H), 5.80 (dqd, J=
15.4, 6.5, 0.7 Hz, 1H; CH3CH), 5.56 (ddq, J=15.4, 8.7, 1.7 Hz, 1H;
SO2CHCH), 4.21 (q, J=14.1 Hz, 2H; SO2CH2), 3.53 (dq, J=8.5, 7.1 Hz,
1H; SO2CH), 1.81 (dd, J=6.4, 1.5 Hz, 3H; CH3), 1.43 ppm (d, J=7.1 Hz,
3H; SO2CHCH3); 13C NMR (75 MHz, CDCl3): d=133.5 (CH3CH), 130.9
(2C; Ar-C), 128.9 (2C; Ar-C), 128.8 (Ar-C), 127.8 (Ar-C), 125.0
(SO2CHCH), 59.8 (SO2CH), 56.0 (SO2CH2), 18.2 (CH3), 12.8 ppm
[12] J. Muzart, A. Riahi, J. P. Pete, J. Organomet. Chem. 1985, 280, 269–
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Pattenden, D. A. Whiting, J. Chem. Soc. Perkin Trans. 1 1975, 897–
913.
~
(SO2CHCH3); IR (neat): n=2033, 1980, 2938, 1965, 1495, 1455, 1298,
1256, 1116, 1020, 969, 872, 772, 722, 698, 609, 546 cmꢀ1; MS (EI, 70 eV):
m/z (%): 225 (3) [M+H+], 197 (1), 160 (5), 131 (1), 118 (1), 91 (26), 69
(100), 53 (1), 41 (22) ; HRMS (ESI): m/z calcd for C12H16O2S+Na:
247.0763, found: 247.0758.
1-[(R)-3,7-Dimethylocta-1,6-dien-3-ylsulfonyl]benzene (61):[29e] Sulfone
61 was prepared according to GPV. After column chromatography (pe-
troleum ether/ethyl acetate 5/1) the product was obtained as a colorless
[19] B. M. Trost, R. Ghadiri, J. Am. Chem. Soc. 1986, 108, 1098–1100.
Chem. Eur. J. 2011, 17, 10417 – 10430
ꢂ 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemeurj.org
10429

B. Plietker and M. Jegelka
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Received: April 6, 2011
Published online: August 4, 2011
10430
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