Sulfinate-Organocatalyzed (3+2) Annulation of Allenyl Sulfones with 1,1-Dicyano Olefins in the Presence of a Quaternary Ammonium Phase Transfer Agent

Article abstract of DOI:10.1002/adsc.201800466

The benzenesulfinate-catalyzed (3+2) annulation between allenyl sulfones and aryl(alkyl)idenemalononitriles has been developed under mild phase transfer conditions, affording a breadth of functionalized sulfonyl cyclopentenes in good to excellent yields (

Full text of DOI:10.1002/adsc.201800466

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DOI: 10.1002/adsc.201800466
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Sulfinate-Organocatalyzed (3+2) Annulation of Allenyl Sulfones
with 1,1-Dicyano Olefins in the Presence of a Quaternary
Ammonium Phase Transfer Agent
Thomas Martzel,a Jean-Franc¸ois Lohier,a Annie-Claude Gaumont,a Jean-
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b
a,
`
´
Franc¸ois Briere, and Stephane Perrio *
a
Normandie Univ, ENSICAEN, UNICAEN, CNRS, LCMT, 14000 Caen, France
Fax: (+33)-2-3145-2865; phone: (+33)-2-3145-2884
E-mail: stephane.perrio@ensicaen.fr
Normandie Univ, INSA Rouen, UNIROUEN, CNRS, COBRA, 76000 Rouen, France
b
17 Received: April 11, 2018; Revised: May 7, 2018; Published online: &&&, &&&&
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the reactivity of the a- or g-substituted allenyl
Abstract: The benzenesulfinate-catalyzed (3+2)
annulation between allenyl sulfones and aryl(alkyl)-
idenemalononitriles has been developed under mild
phase transfer conditions, affording a breadth of
functionalized sulfonyl cyclopentenes in good to
excellent yields (22 examples, 49–99%) and high
diastereoselectivities. These adducts were likely
generated, via an allylsulfone anion featuring a
quaternary ammonium cation.
sulfones[6] has being seldom examined.
Following our current interest in exploring nucleo-
philic sulfinate catalysis,[9] herein we report an effi-
cient (3+2) annulation reaction of allenyl sulfones 1
(R1, R2) with substituted cyano-based olefins[10]
2
(EWG, R3), which proceeds under mild conditions and
with operational simplicity (Scheme 1, equation 2).
The protocol takes profit of phase transfer conditions,
which probably allows the formation of a lipophilic
À
sulfinate ammonium (PhSO2 R4N+) species and
Keywords: phase-transfer catalysis; sulfinate; annu-
lation; allene; carbocycle
enhances the reactivity of the anionic intermediates
successively formed.[11,12] This investigation also re-
1 Introduction
37 The (3 +2) annulation reaction between electron-poor
38 allenes and Michael acceptors has emerged as a
39 powerful strategy for the construction of cyclopentene
40 derivatives.[1] This synthetic sequence has been pro-
41 moted by a catalytic amount of a tertiary phosphine as
42 Lewis base, and paved the way for efficient syntheses
43 of medicinally important architectures.[2] At the end of
44 the 1980s, the group of Padwa described a unique and
45 complementary process with parent allenyl sulfone in
46 the preÀsence of a benzenesulfinate organocatalyst[3]
47 (PhSO2 Na+), which resulted in the formation of
48 versatile sulfonyl cyclopentene platforms (Scheme 1,
49 equation 1).[4,5] This sequence was initiated by the
50 catalytic addition of the sulfur catalyst on the central
51 carbon atom of the cumulene to generate the highly
Scheme 1. Background and objectives.
52 reactive allyl sulfone anion I. Notwithstanding the vealed an original reactivity pattern, which involves a
53 synthetic values offered by this strategy, very few subtle prototropic shift and leads, in most cases, to the
54 developments have been described so far.[6–8] To date formation of products of structural type 4. Very
55 and to the best of our knowledge, intermolecular recently, while the manuscript was in progress,
56 examples are confined to non-substituted Michael Kuwano’s research group briefly reported the related
57 acceptors (if the few cyclic ones[6,7] are excluded) and annulation reaction of parent allenyl sulfone (R1 =
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R2 =H) with arylidenemalononitriles (EWG=CN, noticed in dichloromethane or toluene solutions, the
R3 =Ar), initiated by an N-heterocyclic carbene cata- formation of the side-product 5 was not totally
lyst.[13]
suppressed (entries 2 and 3). Gratifyingly, a complete
selectivity was achieved in acetonitrile, which resulted
in the isolation of 4aa in an 84% yield (entry 4).
Furthermore, the reaction is particularly faster in this
2 Results and Discussion
We commenced our study (Table 1) by investigating medium (4 h versus 24 h in THF for example). A
parent allenyl sulfone 1a (1.5 equiv.) and 2-benzylide- similar efficiency of the process was still observed by
nemalononitrile 2a in the presence of catalytic decreasing the amount of allene 1a to 1.2 equivalent
10 amounts of sodium benzenesulfinate and n-tetrabuty- (entry 5). The beneficial effect of the PT-catalyst was
11 lammonium bromide (10 mol% each). The reaction then clearly pointed. The yield for 4aa dropped to
12 was initially conducted at room temperature for 24 h 57% without the addition of n-Bu4NBr, along with the
13 in THF as solvent and delivered cleanly two products, appearance of unwanted side-product 5 (entry 6).
14 which were readily separated by column chromatog- Finally, the use of Me3BnNCl led to a faster process,
15 raphy on silica gel (entry 1). Standard spectral identi- in which the reagents were consumed within 20 min
16 fication techniques rapidly showed that none of them (entry 7). However, the desired product 4aa was
17 corresponds to the anticipated cycloadduct 3aa. The isolated only in a 63% yield, with concomitant
18 structures were unambiguously assigned by single formation of 5. Interestingly, the procedure does not
19 crystal X-ray analyses (see Supporting Information). require a large excess nor dropwise addition of allenyl
20 The major compound 4aa, isolated in a 67% yield, is sulfone 1a as already mentioned,[8a] thus exhibiting the
21 position isomer of 3aa, in which the carbon-carbon specific and high reactivity of benzylidenemalononi-
22 double bond is conjugated with the phenyl group. The trile 2a under the PT conditions.
23 minor compound, produced in a 20% yield, was
The reaction outcome of the process is highly
dependent on the nature of the activating groups of
the electron deficient alkene employed, as outlined in
Scheme 2. An experiment carried out with the related
cyanoester 6a showcased the formation of the adduct
7, with a diastereoselective ratio >99:1 in an 80%
yield. The carbon-carbon double bond in 7 is con-
jugated with the sulfur substituent, and not with the
phenyl group as previously observed with bis-nitrile
2a. The observed stereochemical outcome for 7
reflects perfectly the trans relationship of the phenyl
substituent and the ester group in the starting olefin
6a.[15] It can be interpreted by a (3+2) cycloaddition
type mechanism taking place in a concerted fashion or
a non-concerted manner (1,4-addition followed by a
formal SN2’ reaction), incorporating a rapid cycliza-
tion step.[16] In contrast, coumarine 6b and malonate
derivative 6c were unreactive under identical con-
ditions. A similar failure was also observed with
cinnamonitrile 6d and ethyl cinnamate 6e. This result
clearly highlights the specific reactivity of the 1,1-
24 identified as the disulfonyl cyclopentene 5.[14]
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Table 1. Proof and reaction optimization.[a]
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Entry
R4NX
Solvent,
time (h)
4aa/5[b]
Isolated
yield (%)
1
2
3
n-Bu4NBr
n-Bu4NBr
n-Bu4NBr
n-Bu4NBr
n-Bu4NBr
–
THF, 24
CH2Cl2, 24
PhMe, 4
MeCN, 4
MeCN, 16
MeCN, 16
MeCN, 0.33
76/24
89/11
84/16
>99/1
>99/1
65/35
67/33
67 (20)[c]
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78
84
82
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63
4
5[d]
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Me3BnNCl
[a]
Reaction performed with 2 a (0.1 mmol) and 1 a
(1.5 equiv.) in solvent (1 mL) in the presence of
PhSO2Na/R4NX catalytic system (10 mol%).
[b] Ratio determined by H NMR on the crude product.
1
[c] Isolated yield of 5 under brackets.
[d] With 1.2 equiv. of 1a.
Optimization of the reaction conditions was then
56 investigated. Although significant improvements for
57 the conversion into 4aa, up to a 78% yield, were
Scheme 2. Comparison with other Michael acceptors 6.
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diactivated olefins and also the crucial requirement of with 2a and provided 4aa without any loss of
at least one cyano group.
efficiency (80% yield versus 82% previously).
We then explored the generality of the sulfinate-
Pleasingly, alkylidenemalononitriles turned out to
mediated annulation reaction in the presence of allene be compatible substrates, but a markedly different
1a. As shown in Table 2, arylidene derivatives 2b–e reaction outcome, leading exclusively to products 3,
with various substitution on the benzene ring (4-Cl, 4- was observed (Table 3). The conjugation of the
OMe, 4-NO2, 2-Cl) were tolerated, leading to the carbon-carbon double bond with the sulfonyl group
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corresponding cyclopentene targets 4ab–4ae with was determined by H NMR analyses. This was also
yields higher than 72%. A lower yield of 50% (4af) confirmed in the case of the t-Bu derivative 3ao by an
10 was obtained with a methoxy substituent in the ortho X-ray experiment (see Supporting Information). THF
11 position, but a slight improvement to a 57% yield was turned out to be the suitable reaction solvent in this
12 obtained when switching to THF as solvent. 2- series, providing better yields. As the most prominent
13 Naphthyl and [2.2]paracyclophan-4-yl derived accept- example, compound 3am displaying an n-propyl group
14 ors can also participate in the process (4ag and 4ah, was produced in a 61% yield in THF, whereas only
15 86 and 80% respectively). Introduction of heterocyclic trace amounts were detected in a CH3CN medium.
16 motifs was also successful, as exemplified by products
17 flanked with furan (4ai, 84%), thiophene (4aj, 74%)
18 or indole (4ak, 77%) rings. Moreover, ferrocene 4al
Table 3. Extension to alkylidenemalononitriles.[a,b]
19 was synthesized in a 70% yield and its structure was
20 confirmed by a single-crystal X-ray diffraction analy-
21 sis. In order to highlight the practicality of the
22 protocol, a 1.1 mmol scale reaction was carried out
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Table 2. Substrate scope with allenyl sulfone 1a.[a,b]
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[a] Reaction performed with 2 (0.1 mmol) and 1a (1.2 equiv.)
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in THF (1 mL) in the presence of PhSO2Na/n-Bu4NBr
catalytic system (10 mol%).
[b] Isolated yields.
[c] Reaction carried out in CH3CN under brackets.
Next, we wondered whether g-methyl allenyl
sulfone 1b could also be exploited in the process
(Table 4). Reaction of the five (het)arylidenemaloni-
triles 2 in the presence of PhSO2Na/n-Bu4NBr as the
catalytic system in THF led to the isomerized adducts
4, with chemical yields in the range of 49 to 77%. A
control experiment carried out with 2a showed that
no reaction took place without the ammonium cata-
lyst. A single diastereoisomer of 4, displaying a trans
geometry, was invariably formed, as confirmed by an
X-ray structural analysis of 4ba (R1 =Ph). In contrast,
the three alkylidene derivatives 2m–o we tested (R1 =
n-Pr, Cy, t-Bu) were not accommodated in this series.
A similar failure was observed with the Michael
acceptors 6a–c displaying an ester function as activat-
ing group (see Scheme 2 for the structures).
[a] Reaction performed with 2 (0.1 mmol) and 1a (1.2 equiv.)
in CH3CN (1 mL) in the presence of PhSO2Na/n-Bu4NBr
catalytic system (10 mol%).
[b] Isolated yields.
[c] Reaction on a 1.1 mmol scale under brackets.
[d] Under brackets reaction carried out in THF.
[e] With Me3BnNCl as the PT-catalyst.
We finally turned our attention to a-methyl allenyl
sulfone 1c, for which the transformation was success-
ful. However, more contrasted and unpredictable
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Table 4. Extension to g-methyl allenyl sulfone 1b.[a,b]
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2
3
both isomers 3ca and 4ca were unequivocally proven
by single-crystal X-ray analyses. The effect of the PT-
catalyst was again ascertained, as only a 21% yield of
3ca was obtained after 24 h without n-Bu4NBr
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(3ca:4ca, >99:1 ratio).
A
rapid screening of
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ammonium salts (see Supporting Information) showed
that n-Bu4NBr was the optimal catalyst, while the
anion had a dramatic impact on 3ca and 4ca
distribution. Interestingly, n-Bu4NOAc furnished ex-
clusively the isomerized compound 4ca in an 89%
yield. Conditions using n-Bu4NBr also led to 3cc
displaying a 4-methoxyphenyl substituent (78% yield).
In contrast, the isomerized adduct 4cj was produced
directly in the presence of n-Bu4NBr in an 82% yield
from the 2-thienyl malononitrile 2j.
Based on these results and literature back-
ground,[4,6] we propose the catalytic cycle outlined in
Figure 1. The process probably begins with the extrac-
tion of the sulfinate catalyst into the organic phase
through sodium/ammonium counterion exchange. The
equilibrated addition of the lipophilic ammonium
sulfinate on the electrophilic b carbon atom of 1
would generate a small amount of allyl sulfone anion
II. Regioselective conjugate addition of 2, through the
carbon centre in a-position to the sulfone moiety (II)
would provide the conjugate addition intermediate
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20 [a] Reaction performed with 1b (0.1 mmol) and 2 (1.5 equiv.)
in THF (1 mL) in the presence of PhSO2Na/n-Bu4NBr
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catalytic system (10 mol%).
[b] Isolated yields.
[c] No reaction without n-Bu4NBr.
27 results were observed for the structure of the isolated III, which would then undergo cyclization to generate
28 product (Table 5). The reaction with benzylidenemalo- the sulfonyl anion IV. Elimination of the sulfinate can
29 nonitrile 2a led to the adduct 3ca in an excellent 85% take place at this stage to furnish adduct 3 (route A,
30 yield, along with trace amounts of the readily separa- R3 =alkyl and R1 =R2 =H). When R3 =(het)aryl, a
31 ble isomer 4ca (3ca:4ca, 96/4 ratio). The structures of spontaneous intramolecular proton transfer is specu-
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lated, leading to the benzylic carbanion V (route B,
R1 =R2 =H), from which PhSO2À would be released to
afford the isomerized product 4.[17] In the g-methyl
series (R2 =Me), the proton shift proceeds with
complete diastereoselectivity in favor of a trans
configuration, probably to minimize steric hindrance.
Table 5. Extension to a-methyl allenyl sulfone 1c.[a,b]
[a] Isolated yields.
[b] Reaction performed with 1c (0.1 mmol) and 2 (1.5 equiv.)
in THF (1 mL) in the presence of PhSO2Na/n-Bu4NBr
catalytic system (10 mol%).
[c] Under brackets, reaction performed without n-Bu4NBr.
[d] Reaction carried out with n-Bu4NOAc (10 mol%) as PT-
catalyst, instead of n-Bu4NBr (10 mol%).
Figure 1. Proposed sulfinate-mediated catalytic cycle under
PT conditions.
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Competition between routes A and B is observed lective, in the presence of chiral quaternary
from the a-methyl precursor 1c, the selectivity being ammonium salts, unfortunately failed and led to low
highly dependent on the nature of 2. In some case, we asymmetric inductions.[20] Further studies to expand
cannot also rule out isomerization of the kinetic synthetic approaches mediated by sulfinate catalysts
product 3 into the thermodynamic isomer 4 displaying are ongoing in our laboratory.
an aryl-conjugated C=C bond. This option could
account of the role of AcOÀ as a basic proton-shift
promoter (Table 5).
Experimental Section
To illustrate the potential of our substrates, some General
10 representative transformations were performed
11 (Scheme 3).
Dry THF, CH2Cl2 and acetonitrile were obtained by a
passage down an activated alumina column. All other
reagents and solvents were used as purchased from commer-
cial sources. All reactions were performed in oven-dried
glassware, under an atmosphere of dry nitrogen. Low
reaction temperatures stated were those of the reaction
mixtures. Reactions were purified by column chromatogra-
phy with silica gel Si 60 (0.040–0.063 nm). Thin layer
chromatography was carried out on silica gel 60 F254
(1.1 mm) with spot detection under UV light and/or through
KMnO4 oxidation. Melting points were obtained on a
capillary apparatus and are uncorrected. All chemical shifts
(d) and coupling constants (J) in the NMR spectra are
quoted in parts per million (ppm) and Hertz (Hz) respec-
tively. The following abbreviations are used to designate the
multiplicity of the signals: s=singlet; d=doublet; t=triplet;
m=multiplet; br=broad; app=apparent and combinations
thereof. The chemical shifts are calibrated to TMS (d H 0.00)
or residual proton and carbon resonances of the solvent
CDCl3 (d H 7.26 and d C 77.16). IR spectra were recorded
on an ATR-FT-IR instrument equipped with a diamond
ATR probe. Wavenumbers are quoted in cmÀ1. Low
resolution mass spectra were recorded on a GC/MS/MS
instrument and only peaks of an intensity >10% (except
decisive ones) are listed. High resolution mass spectra
(HRMS) were recorded on a QTOF LC/MC instrument. X-
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Scheme 3. Synthetic applications of 4aa.
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Treatment of sulfonyl cyclopentene 4aa with m-
26 CBPA (3 equiv.) led to the epoxide 8 as a single
27 diastereoisomer in an 84% yield (See Supporting
28 Information for the stereochemical assignment based
1
29 on the recorded H NMR data). Conversion into the
30 methyl ester 9 could also be achieved in a 70% yield
31 by solvolysis[18] of one of the cyano groups in methanol
32 in the presence of K2CO3, thus broadening the use of
33 dicyano compounds to cyano-ester derivatives. Worthy
34 of note is that product 9 is an isomer of cyclopentene
35 7, previously obtained in Scheme 2 from cyanoester
36 6a.
ray diffraction experiments were performed with
a
graphiteÀmonochromatized Mo Ka radiation on a CCD area
detector diffractometer.
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3 Conclusion
Typical Procedures for (3+2) Annulations with
Allenes 1a and 1b
40 In summary, we have successfully developed
a
41 straightforward (3+2) annulation, under phase trans-
42 fer conditions, between allenyl sulfones and 2-substi-
43 tuted-1,1-dicyano olefins in the presence of catalytic
44 PhSO2Na. The reaction provides a facile access to
45 original sulfonyl cyclopentenes and extends thereby
46 the initial Padwa process with a unique proton shift.
47 The salient features of the methodology include mild
48 reaction conditions, operational simplicity (no need of
49 a syringe pump for a slow addition of the allene),
50 atom-economy, wide substrate scope with regard to
51 both reaction partners, high chemo- and diastereose-
52 lectivity and good yields of isolated product. The
53 reaction is a valuable complement to currently existing
54 methods for accessing synthetically useful multifunc-
55 tional cyclopentenes[1,10,19] and has also potential to be
56 further applied through manipulation of the functional
57 groups. First attempts to render the process enantiose-
Procedure A in MeCN: Allenyl sulfone 1a or 1b (1.2 equiv.),
Michael acceptor 2 (1 equiv.), n-Bu4NBr (10 mol%) were
diluted in MeCN (0.1 M) and PhSO2Na (10 mol%) was
added. After stirring at room temperature for 16 hours, the
reaction mixture was concentrated under reduced pressure
and directly purified by column chromatography on silica gel
to afford the pure cyclopentene 3 or 4.
Procedure B in THF: Allenyl sulfone 1a or 1b (1.5 equiv.),
Michael acceptor 2 or 6a (1 equiv.), n-Bu4NBr (10 mol%)
were diluted in THF (0.1 M) and PhSO2Na (10 mol%) was
added. After stirring at room temperature for 24 hours, the
reaction mixture was concentrated under reduced pressure
and directly purified by column chromatography on silica gel
to afford the pure cyclopentene 3 or 4.
2-Phenyl-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarboni-
trile (4aa): According to procedure A, cyclopentene 4aa was
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obtained from allene 1a (21.6 mg, 0.12 mmol), malononitrile
derivative 2a (15.4 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in MeCN
(1 mL). Column chromatography with petroleum ether/
AcOEt/CH2Cl2 =7/1.5/1.5. Yield 82% (27 mg, 0.082 mmol).
The reaction was repeated on a larger scale, starting with 1a
(200 mg, 1.11 mmol), 2a (258 mg, 1.67 mmol), n-Bu4NBr
(36 mg, 0.11 mmol) and PhSO2Na (20 mg, 0.11 mmol) in
MeCN (10 mL). Yield 80% (267 mg, 0.799 mmol). Beige
malononitrile derivative 2d (19.9 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
MeCN (1 mL). Column chromatography with petroleum
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ether/AcOEt/CH2Cl2 =6/2/2.
Yield
73%
(27.7 mg,
0.073 mmol). Pale yellow solid, mp: 65–668C. 1H NMR
(400 MHz, CDCl3): d 3.21 and 3.31 (AB part of ABX system,
3
3
3
2JAB =15.0, JAX =5.4 and JBX =8.3, 1H each), 4.71 (ddd, J=
2.6, 5.4 and 8.3, 1H), 6.63 (d, 3J=2.6, 1H), 7.65–7.69 (m, 2H),
7.77–7.80 (m, 3H), 7.94–7.96 (m, 2H), 8.33–8.35 (m, 2H). 13C
NMR (100 MHz, CDCl3): d 38.4, 40.2, 69.8, 112.9, 113.9,
124.6 (2C), 127.9 (2C), 128.9 (2C), 130.1 (2C), 130.3, 135.2,
135.3, 136.0, 141.1, 148.8. IR (neat, ATR probe, cmÀ1): 2160,
1977, 1599, 1518, 1447, 1347, 1308, 1149, 1083, 847. HRMS
(ESI): Calculated for C19H13N3O4SNa [(M+Na)+]: 402.0524,
found: 402.0520.
1
solid, mp: 158–1598C. H NMR (400 MHz, CDCl3): d 3.20
2
3
3
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and 3.25 (AB part of ABX, JAB =15.0, JAX =5.5 and JBX
=
3
8.4, 1H each), 4.67 (ddd, J=2.6, 5.5 and 8.4, 1H), 6.44 (d,
3J=2.6, 1H), 7.46–7.49 (m, 3H), 7.58–7.70 (m, 4H), 7.73–7.77
13 (m, 1H), 7.92–7.95 (m, 2H). 13C NMR (100 MHz, CDCl3): d
38.4, 40.1, 69.8, 113.5, 114.5, 126.0, 126.8 (2C), 129.0 (2C),
129.2, 129.4 (2C), 129.9 (2C), 130.8, 135.0, 136.0, 143.0. IR
(neat, ATR probe, cmÀ1): 2913, 2438, 2160, 2030, 1977, 1447,
1307, 1222, 1139, 1087. HRMS (ESI): Calculated for
C19H14N2O2SNa [(M+Na)+]: 357.0674, found: 357.0670.
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2-(2-Chlorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-
dicarbonitrile (4ae): According to procedure A, cyclopen-
tene 4ae was obtained from allene 1a (21.6 mg, 0.12 mmol),
malononitrile derivative 2e (18.8 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
MeCN (1 mL). Column chromatography with petroleum
ether/AcOEt=7.5/2.5. Yield 77% (28.4 mg, 0.077 mmol).
2-(4-Chlorophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-
dicarbonitrile (4ab): According to procedure A, cyclopen-
tene 4ab was obtained from allene 1a (21.6 mg, 0.12 mmol),
malononitrile derivative 2b (18.8 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
MeCN (1 mL). Column chromatography with petroleum
ether/AcOEt/CH2Cl2 =6.5/1.75/1.75. Yield 79% (29.2 mg,
1
White solid, mp: 143–1448C. H NMR (400 MHz, CDCl3): d
3
3.19–3.29 (m, 2H), 4.70–4.75 (m, 1H), 6.33 (d, J=2.2, 1H),
7.34–7.42 (m, 2H), 7.47–7.51 (m, 2H), 7.64–7.67 (m, 2H),
7.75–7.79 (m, 1H), 7.95–7.97 (m, 2H). 13C NMR (100 MHz,
CDCl3): d 37.9, 43.0, 70.0, 113.0, 113.9, 127.3, 128.9, 129.2
(2C), 129.7, 129.9 (2C), 130.7, 131.4, 133.0, 133.8, 135.1,
136.0, 139.5. IR (neat, ATR probe, cmÀ1): 2927, 1470, 1448,
1318, 1147, 1083, 1042, 757, 727, 714. HRMS (ESI):
Calculated for C19H13ClN2O2SNa [(M+Na)+] with 35Cl
isotope: 391.0284, found: 391.0278.
1
0.079 mmol). White solid, mp: 72–738C. H NMR (400 MHz,
2
CDCl3): d 3.18 and 3.26 (AB part of ABX system, JAB
=
3
3
15.0, JAX =5.2 and JBX =8.4, 1H each), 4.64–4.69 (m, 1H),
6.43 (d, J=2.4, 1H), 7.43–7.45 (m, 2H), 7.53–7.55 (m, 2H),
3
7.62–7.66 (m, 2H), 7.73–7.77 (m, 1H), 7.92–7.94 (m, 2H). 13C
NMR (100 MHz, CDCl3): d 38.4, 40.1, 69.8, 113.3, 114.3,
126.7, 127.7, 128.1 (2C), 129.0 (2C), 129.7 (2C), 130.0 (2C),
135.1, 136.0, 137.1, 141.9. IR (neat, ATR probe, cmÀ1): 2924,
2159, 1977, 1594, 1493, 1447, 1404, 1307, 1148, 1084. HRMS
(ESI): Calculated for C19H13ClN2O2SNa [(M+Na)+] with
35Cl isotope: 391.0284, found: 391.0283.
2-(2-Methoxyphenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-
dicarbonitrile (4af): According to procedure A, cyclopentene
4af was obtained from allene 1a (27 mg, 0.15 mmol),
malononitrile derivative 2f (18.4 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
THF (1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =6.5/1.75/1.75. Yield 57% (20.7 mg, 0.057 mmol).
2-(4-Methoxyphenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-
dicarbonitrile (4ac): According to procedure A, cyclopen-
tene 4ac was obtained from allene 1a (21.6 mg, 0.12 mmol),
malononitrile derivative 2c (18.4 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
MeCN (1 mL). Column chromatography with petroleum
ether/AcOEt/CH2Cl2 =6.5/1.75/1.75. Yield 83% (30.2 mg,
0.083 mmol). Orange solid, mp: 144–1458C. 1H NMR
(400 MHz, CDCl3): d 3.17 and 3.23 (AB part of ABX system,
1
White solid, mp: 139–1408C. H NMR (400 MHz, CDCl3): d
3
3.09 and 3,13 (AB part of ABX system, 2JAB =14, JAX
=
3JAX =7.4, 1H each), 3.92 (s, 3H), 4.67 (dt, J=2.3 and 7.4,
1H), 6.51 (d, J=2.3, 1H), 6.98–7.04 (m, 2H), 7.41–7.45 (m,
3
3
2H), 7.63–7.67 (m, 2H), 7.73–7.77 (m, 1H), 7.94–7.96 (m,
2H). 13C NMR (100 MHz, CDCl3): d 39.4, 42.0, 55.0, 69.2,
111.7, 113.9, 115.0, 118.8, 121.2, 128.1, 129.0 (2C), 129.8 (2C),
129.9, 132.1, 134.9, 136.4, 157.0. IR (neat, ATR probe, cmÀ1):
2160, 2030, 1599, 1489, 1448, 1310, 1265, 1151, 1087, 1017.
HRMS (ESI): Calculated for C20H16N2O3SNa [(M+Na)+]:
387.0779, found: 387.0774.
3
3
2JAB =15.0, JAX =5.4 and JBX =8.2, 1H each), 3.85 (s, 3H),
3
3
4.67 (ddd, J=2.6, 5.4 and 8.2, 1H), 6.30 (d, J=2.6, 1H),
6.95–6.97 (m, 2H), 7.53–7.56 (m, 2H), 7.61–7.65 (m, 2H),
7.72–7.76 (m, 1H), 7.91–7.94 (m, 2H). 13C NMR (100 MHz,
CDCl3): d 38.4, 40.0, 55.5, 69.9, 113.6, 114.7 (3C, signals
overlapping), 121.7, 123.3, 128.3 (2C), 129.1 (2C), 129.9 (2C),
135.0, 136.0, 142.5, 161.5. IR (neat, ATR probe, cmÀ1): 2452,
2159, 1976, 1644, 1480, 1446, 1308, 1146, 1083, 1022. HRMS
2-(2-Naphthyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicar-
bonitrile (4ag): According to procedure A, cyclopentene 4ag
was obtained from allene 1a (21.6 mg, 0.12 mmol), malono-
nitrile derivative 2g (20.4 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in MeCN
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =6.5/1.75/1.75. Yield 86% (33.2 mg, 0.086 mmol).
52 (ESI): Calculated for C20H16N2O3SNa [(M+Na)+]: 387.0779,
found: 387.0775.
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2-(4-Nitrophenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-di-
carbonitrile (4ad): According to procedure A, cyclopentene
4ad was obtained from allene 1a (21.6 mg, 0.12 mmol),
1
Yellow solid, mp: 186–1878C. H NMR (400 MHz, CDCl3): d
3.24 and 3.31 (AB part of ABX system, 2JAB =15.0, 3JAX =5.4
Adv. Synth. Catal. 2018, 360, 1–12
6
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3
3
3
3
3
and JAX =8.4, 1H each), 4.72 (ddd, J=2.6, 5.4 and 8.4, 1H),
15.3, JAX =4.7 and JBX =8.6, 1H each), 4.64 (ddd, J=2.8,
1
2
3
4
5
6
7
8
9
3
3
3
6.57 (d, J=2.6, 1H), 7.55–7.60 (m, 2H), 7.62–7.66 (m, 3H),
4.7 and 8.6, 1H), 6.25 (d, J=2.8, 1H), 7.11 (dd, J=3.8 and
5.1, 1H), 7.43–7.46 (m, 2H), 7.61–7.65 (m, 2H), 7.73–7.76 (m,
1H), 7.90–7.93 (m, 2H). 13C NMR (100 MHz, CDCl3): d 38.1,
40.4, 70.2, 113.2, 114.3, 123.9, 128.2, 128.5, 128.9, 129.1 (2C),
129.9 (2C), 132.1, 135.1, 135.7, 136.8. IR (neat, ATR probe,
cmÀ1): 3106, 2904, 2160, 1448, 1307, 1225, 1138, 1085, 864,
731. HRMS (ESI): Calculated for C17H12N2O2S2Na [(M+
Na)+]: 363.0238, found: 363.0237.
7.73–7.77 (m, 1H), 7.85–7.87 (m, 1H), 7.90–7.97 (m, 4H),
8.08–8.10 (m, 1H). 13C NMR (100 MHz, CDCl3): d 38.6, 40.0,
70.0, 113.6, 114.7, 123.4, 126.1, 126.4, 126.9, 127.3, 127.8,
128.0, 128.9, 129.1 (2C), 129.4, 129.9 (2C), 132.9, 133.9, 135.1,
136.0, 142.9. IR (neat, ATR probe, cmÀ1): 2925, 2159, 1446,
1308, 1147, 1083, 854, 814, 751, 722. HRMS (ESI): Calculated
for C23H16N2O2SNa [(M+Na)+]: 407.0830, found: 407.0825.
2-([2.2]Paracyclophan-4-yl)-4-(phenylsulfonyl)cyclopent-2-
ene-1,1-dicarbonitrile (4ah): According to procedure A,
cyclopentene 4ah was obtained from allene 1a (21.6 mg,
0.12 mmol), malononitrile derivative 2h (28.4 mg, 0.1 mmol),
n-Bu4NBr (3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg,
0.01 mmol) in MeCN (1 mL). Column chromatography
pentane/AcOEt/CH2Cl2 =7/1.5/1.5. Yield 80% (37 mg,
0.080 mmol). The product was obtained as a mixture of two
non separable diastereoisomers (dr=50:50). Yellow solid,
mp: 112–1138C. 1H NMR (400 MHz, CDCl3): d 2.97–3.25 (m,
9.5H), 3.39 (ddd, J=3.9 9.2 and 13.4, 0.5H), 4.68–4.75 (m,
1H), 6.28 (d, J=2.3, 0.5H), 6.33 (d, J=2.3, 0.5H), 6.35–6.37
(m, 0.5H), 6.43–6.47 (m, 1H), 6.50–6.55 (m, 3H), 6.62–6.69
(m, 2.5H), 7.67–7.73 (m, 2H), 7.77–7.83 (m, 1H), 8.00–8.04
(m, 2H). 13C NMR (100 MHz, CDCl3): d 34.6, 34.7, 35.0,
35.18, 35.22, 35.4, 35.6, 37.8, 38.2, 41.4, 43.5, 69.8, 70.1, 113.1,
113.7, 114.2, 114.5, 128.1, 128.4, 128.90, 128.95, 129.01,
129.11, 130.0, 130.2, 130.6, 131.75, 131.80, 132.3, 132.52,
132.56, 132.59, 132.9, 133.2, 135.1, 135.4, 135.6, 136.2, 136.4,
136.6, 136.8, 138.6, 138.76, 138.84, 139.1, 139.4, 139.7, 140.2,
142.4, 144.3. IR (neat, ATR probe, cmÀ1): 2927, 1585, 1446,
1308, 1147, 1083, 903, 815, 721, 688. HRMS (ESI): Calculated
for C29H24N2O2SNa [(M+Na)+]: 487.1456, found: 487.1458.
2-(3-(N-Boc)indolyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-
dicarbonitrile (4ak): According to procedure A, cyclopen-
tene 4ak was obtained from allene 1a (21.6 mg, 0.12 mmol),
malononitrile derivative 2k (29.3 mg, 0.1 mmol), n-Bu4NBr
(3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in
MeCN (1 mL). Column chromatography with petroleum
ether/AcOEt/CH2Cl2 =7/1.5/1.5. Yield 77% (36.4 mg,
0.077 mmol). Yellow solid, mp: 151–1528C. 1H NMR
(400 MHz, CDCl3): d 1.69 (s, 9H), 3.18 and 3.24 (AB part of
10
11
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13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
2
3
3
ABX system, JAB =15.2, JAX =5.0 and JBX =8.4, 1H each),
4.74–4.78 (m, 1H), 6.56 (d, 3J=2.5, 1H), 6.54 (dd, 3J=1.7 and
3
3
3
3.5, 1H), 6.84 (d, J=3.5, 1H), 7.35–7.46 (m, 2H), 7.60–7.76
(m, 4H), 7.94–7.96 (m, 2H), 8.10 (s, 1H), 8.24–8.26 (m, 1H).
13C NMR (100 MHz, CDCl3): d 28.1 (3C), 37.4, 41.2, 70.9,
85.3, 110.7, 113.6, 114.8, 115.9, 119.7, 123.9, 124.6, 125.8,
126.0, 127.5, 129.2 (2C), 129.9 (2C), 135.0, 135.7, 136.1, 148.8
(1 signal missing, probably overlapping with another one).
IR (neat, ATR probe, cmÀ1): 2159, 1737 (C=O), 1493, 1447,
1370, 1308, 1147, 1083, 826, 722. HRMS (ESI): Calculated
for C26H23N3O4SNa [(M+Na)+]: 496.1307, found: 496.1304.
2-(2-Ferrocenyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,-dicar-
bonitrile (4al): According to procedure A, cyclopentene 4al
was obtained from allene 1a (21.6 mg, 0.12 mmol), malono-
nitrile derivative 2l (26.2 mg, 0.1 mmol), Me3BnNCl (1.9 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in MeCN
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =7.5/1.25/1.25. Yield 70% (31 mg, 0.07 mmol).
2-(2-Furyl)-4-(phenylsulfonyl)cyclopent-2-ene-1,1-dicarboni-
trile (4ai): According to procedure A, cyclopentene 4ai was
obtained from allene 1a (21.6 mg, 0.12 mmol), malononitrile
derivative 2i (14.4 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in MeCN
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =6.5/1.75/1.75. Yield 84% (27.3 mg, 0.084 mmol).
1
Brown solid, mp: 162–1638C. H NMR (400 MHz, CDCl3): d
3.10 and 3.21 (AB part of ABX system, 2JAB =15.2, 3JAX =4.2
and 3JBX =8.5, 1H each), 4.25 (s, 4H), 4.41–4.49 (m, 3H),
1
3
Orange solid, mp: 66–678C. H NMR (400 MHz, CDCl3): d
4.61–4.65 (m, 2H), 6.05 (d, J=2.1, 1H), 7.64–7.68 (m, 2H),
3.16 and 3.26 (AB part of ABX system, 2JAB =15.3, 3JAX =4.6
7.74–7.78 (m, 1H), 7.94–7.96 (m, 2H). 13C NMR (100 MHz,
CDCl3): d 38.4, 40.0, 67.1, 67.7, 70.2, 70.8 (4C), 70.9, 71.7,
72.7, 114.1, 115.1, 119.9, 129.1 (2C), 129.8 (2C), 134.8, 136.5,
144.2. IR (neat, ATR probe, cmÀ1): 2925, 1625, 1450, 1306,
1292, 1155, 1075, 1034, 1000, 727. HRMS (ESI): Calculated
for C23H18N2O2SFe [(M+H)+]: 442.0438, found: 442.0442.
3
3
and JBX =8.6, 1H each), 4.65 (ddd, J=2.8, 4.6 and 8.6, 1H),
3
3
6.30 (d, J=2.8, 1H), 6.54 (dd, J=1.7 and 3.5, 1H), 6.84 (d,
3J=3.5, 1H), 7.54 (d, J=1.7, 1H), 7.61–7.65 (m, 2H), 7.72–
3
7.76 (m, 1H), 7.91–7.93 (m, 2H). 13C NMR (100 MHz,
CDCl3): d 37.8, 39.0, 70.3, 112.3, 112.4, 113.1, 114.2, 122.6,
129.1 (2C), 129.9 (2C), 132.7, 135.0, 135.9, 144.7, 145.3. IR
(neat, ATR probe, cmÀ1): 2452, 2160, 1977, 1644, 1480, 1447,
1308, 1146, 1083, 1022. HRMS (ESI): Calculated for
C17H12N2O3SNa [(M+Na)+]: 347.066, found: 347.0461.
2-(n-Butyl)-4-(phenylsulfonyl)cyclopent-3-ene-1,1-dicarboni-
trile (3am): According to procedure B, cyclopentene 3am
was obtained from allene 1a (27 mg, 0.15 mmol), malononi-
trile derivative 2m (12 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in THF
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =8/1/1. Yield 61% (18.3 mg, 0.061 mmol). Yellow oil.
4-(Phenylsulfonyl)-2-(2-thienyl)cyclopent-2-ene-1,1-dicarbo-
nitrile (4aj): According to procedure A, cyclopentene 4aj
was obtained from allene 1a (21.6 mg, 0.12 mmol), malono-
nitrile derivative 2j (16 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in MeCN
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =6.5/1.75/1.75. Yield 74% (25.3 mg, 0.074 mmol).
3
1H NMR (400 MHz, CDCl3): d 1.02 (t, J=7.2, 3H), 1.49–
1.58 (m, 2H), 1.70–1.89 (m, 2H), 3.28 (s, 2H), 3.45–3.48 (m,
1H), 6.70–6.71 (m, 1H), 7.59–7.63 (m, 2H), 7.70–7.73 (m,
1H), 7.89–7.91 (m, 2H). 13C NMR (100 MHz, CDCl3): d 13.7,
20.5, 32.6, 38.6, 42.4, 54.8, 113.0, 114.8, 128.0 (2C), 129.8
(2C), 134.6, 137.7, 141.1, 141.7. IR (neat, ATR probe, cmÀ1):
Pale yellow solid, mp: 164–1658C. 1H NMR (400 MHz,
2
CDCl3): d 3.19 and 3.26 (AB part of ABX system, JAB
=
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7
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ÞÞ
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COMMUNICATIONS
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2963, 1599, 1519, 1447, 1320, 1308, 1154, 1082, 846, 754.
HRMS (ESI): Calculated for C16H16N2O2SNa [(M+Na)+]:
323.0830, found: 323.0829.
0.077 mmol). Column chromatography with pentane/AcOEt/
1
2
3
4
5
6
7
8
9
CH2Cl2 =8/1/1. The product was obtained as
a single
1
diastereoisomer (dr>99:1). White solid, mp: 190–1918C. H
NMR (400 MHz, CDCl3): d 1.56 (d, 3J=7.1, 3H), 3.39 (quint,
2-Cyclohexyl-4-(phenylsulfonyl)cyclopent-3-ene-1,1-dicarbo-
nitrile (3an): According to procedure B, cyclopentene 3an
was obtained from allene 1a (27 mg, 0.15 mmol), malononi-
trile derivative 2n (16 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in THF
(1 mL). Column chromatography with petroleum ether/
AcOEt=8/2. Yield 88% (29.8 mg, 0.088 mmol). White solid,
mp: 144–1458C. 1H NMR (400 MHz, CDCl3): d 1.06–1.39 (m,
5H), 1.71–1.90 (m, 5H), 1.98–2.03 (m, 1H), 3.21–3.32 (m,
3H), 6.81 (br s, 1H), 7.59–7.63 (m, 2H), 7.70–7.73 (m, 1H),
7.89–7.91 (m, 2H). 13C NMR (100 MHz, CDCl3): d 25.47,
25.50, 25.6, 30.8, 31.4, 37.5, 39.5, 43.0, 61.0, 113.4, 115.1, 128.0
(2C), 129.8 (2C), 134.6, 137.8, 139.8, 141.9. IR (neat, ATR
probe, cmÀ1): 3093, 2933, 2854, 1623, 1446, 1309, 1158, 1086,
759, 718. HRMS (ESI): Calculated for C19H20N2O2SNa [(M+
Na)+]: 363.1143, found: 363.1140.
3
3
3J=7.1, 1H), 4.24 (dd, J=2.2 and 7.7, 1H), 6.30 (d, J=2.2,
1H), 7.44–7.47 (m, 3H), 7.53–7.58 (m, 2H), 7.63–7.68 (m,
2H), 7.73–7.78 (m, 1H), 7.94–7.98 (m, 2H). 13C NMR
(100 MHz, CDCl3): d 16.2, 45.9, 47.0, 75.1, 112.1, 113.7, 126.2,
126.6 (2C), 129.0 (2C), 129.3 (2C), 129.6, 129.9 (2C), 130.7,
135.0, 136.3, 142.2. IR (neat, ATR probe, cmÀ1): 2451, 2159,
2022, 1977, 1446, 1309, 1218, 1142, 1086, 806. HRMS (ESI):
Calculated for C20H16N2O2SNa [(M+Na)+]: 371.0830, found:
371.0837.
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19
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21
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23
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Trans-(Æ)-2-(4-methoxyphenyl)-5-methyl-4-(phenylsulfonyl)-
cyclopent-2-ene-1,1-dicarbonitrile (4bc): According to proce-
dure B, cyclopentene 4bc was obtained from allene 1b
(19.4 mg, 0.1 mmol), malononitrile derivative 2c (27.6 mg,
0.15 mmol), n-Bu4NBr (3.3 mg, 0.01mmol) and PhSO2Na
(1.8 mg, 0.01 mmol) in THF (1 mL). Yield 65% (24.5 mg,
0.065 mmol). Column chromatography with pentane/AcOEt/
CH2Cl2 =7/1.5/1.5. The product was obtained as a single
2-(tert-Butyl)-4-(phenylsulfonyl)cyclopent-3-ene-1,1-dicarbo-
nitrile (3ao): According to procedure B, cyclopentene 3ao
was obtained from allene 1a (27 mg, 0.15 mmol), malononi-
trile derivative 2o (13.4 mg, 0.1 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in THF
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =8/1/1. Yield 99% (31.3 mg, 0.099 mmol). White
1
diastereoisomer (dr>99:1). Yellow solid, mp: 173–1748C. H
NMR (400 MHz, CDCl3): d 1.56 (d, 3J=7.1, 3H), 3.36 (quint,
3
3J=7.1, 1H), 3.84 (s, 3H), 4.22 (dd, J=2.1 and 7.5, 1H), 6.16
3
(d, J=2.1, 1H), 6.93–6.97 (m, 2H), 7.50–7.53 (m, 2H), 7.63–
7.67 (m, 2H), 7.73–7.77 (m, 1H), 7.94–7.96 (m, 2H). 13C NMR
(100 MHz, CDCl3): d 16.3, 45.8, 47.0, 55.5, 75.3, 112.2, 113.9,
114.7 (2C), 122.0, 123.5, 128.1 (2C), 129.0 (2C), 129.8 (2C),
134.9, 136.3, 141.7, 161.4. IR (neat, ATR probe, cmÀ1): 2927,
2160, 1600, 1517, 1447, 1347, 1308, 1150, 1084, 846. HRMS
(ESI): Calculated for C21H18N2O3SNa [(M+Na)+]: 401.0936,
found: 401.0928.
1
solid, mp: 146–1478C. H NMR (400 MHz, CDCl3): d 1.22 (s,
9H), 3.29–3.34 (m, 3H), 6.80–6.82 (m, 1H), 7.60–7.64 (m,
2H), 7.70–7.74 (m, 1H), 7.89–7.91 (m, 2H). 13C NMR
(100 MHz, CDCl3): d 27.8 (3C), 34.3, 35.8, 43.9, 65.5, 114.6,
115.6, 128.0 (2C), 129.8 (2C), 134.6, 137.8, 140.4, 142.1. IR
(neat, ATR probe, cmÀ1): 2968, 2464, 2160, 1976, 1625, 1317,
1294, 1154, 1106, 887. HRMS (ESI): Calculated for
C17H18N2O2SNa [(M+Na)+]: 337.0987, found: 337.0987.
Trans-(Æ)-2-(2-methoxyphenyl)-5-methyl-4-(phenylsulfonyl)-
cyclopent-2-ene-1,1-dicarbonitrile (4bf): According to proce-
dure B, cyclopentene 4bf was obtained from allene 1b
(19.4 mg, 0.1 mmol), malononitrile derivative 2f (27.6 mg,
0.15 mmol), n-Bu4NBr (3.3 mg, 0.01 mmol) and PhSO2Na
(1.8 mg, 0.01 mmol) in THF (1 mL). Column chromatogra-
phy with pentane/AcOEt/CH2Cl2 =8/1/1. Yield 57%
(21.7 mg, 0.057 mmol). The product was obtained as a single
(1S*,2R*)-1-Cyano-2-phenyl-4-(phenylsulfonyl)cyclopent-3-
enecarboxylic Acid Methyl Ester (7): According to proce-
dure B, cyclopentene 7 was obtained from allene 1a (27 mg,
0.15 mmol), (E)-configured cyanoester derivative 6a
(18.7 mg, 0.1 mmol), n-Bu4NBr (3.3 mg, 0.01 mmol) and
PhSO2Na (1.8 mg, 0.01 mmol) in THF (1 mL). Yield 80%
(29.5 mg, 0.080 mmol). Column chromatography with
pentane/AcOEt/CH2Cl2 =6.5/1.75/1.75. The product was ob-
tained as a single diastereoisomer (dr>99:1). Colorless oil.
1H NMR (400 MHz, CDCl3): d 3.24 (dt, 2J=16.3 and 4J=1.7,
1
diastereoisomer (dr>99:1). White solid, mp: 148–1498C. H
3
NMR (400 MHz, CDCl3): d 1.60 (d, J=6.9, 3H), 3.21–3.29
3
(m, 1H), 3.91 (s, 3H), 4.26 (dd, J=1.9 and 8.7, 1H), 6.31 (d,
3
3J=1.9, 1H), 6.95–7.02 (m, 2H), 7.32 (dd, J=1.5 and 7.7,
1H), 7.38–7.43 (m, 1H), 7.64–7.68 (m, 2H), 7.73–7.77 (m,
1H), 7.95–7.98 (m, 2H). 13C NMR (100 MHz, CDCl3): d 15.1,
47.0, 48.9, 54.9, 73.9, 111.6, 112.6, 114.0, 119.2, 121.2, 128.5,
129.0 (2C), 129.7 (2C), 129.8 (1C), 132.0, 134.9, 136.6, 141.1,
156.9. IR (neat, ATR probe, cmÀ1): 2527, 2160, 1976, 1597,
1489, 1468, 1307, 1268, 1144, 1023. HRMS (ESI): Calculated
for C21H18N2O3SNa [(M+Na)+]: 401.0936, found: 401.0929.
2
4
1H), 3.39 (dt, J=16.3 and J=2.0, 1H), 3.83 (s, 3H), 4.75–
4.78 (m, 1H), 6.77–6.79 (m, 1H), 7.15–7.20 (m, 2H), 7.31–7.40
(m, 3H), 7.61–7.65 (m, 2H), 7.70–7.74 (m, 1H), 7.96–7.98 (m,
46 2H). 13C NMR (100 MHz, CDCl3): d 41.3, 54.4, 55.1, 58.5,
116.5, 128.1 (2C), 128.4 (2C), 129.17 (2C), 129.24, 129.7 (2C),
134.3, 134.8, 138.3, 141.0, 143.2, 167.7. IR (neat, ATR probe,
cmÀ1): 3105, 2160, 1744(C=O), 1447, 1307, 1241, 1151, 1083,
755, 722. HRMS (ESI): Calculated for C20H17NO4SNa [(M+
Na)+]: 390.0776, found: 390.0770.
47
48
49
50
51
52
Trans-(Æ)-2-(2-naphthyl)-5-methyl-4-(phenylsulfonyl)cyclo-
pent-2-ene-1,1-dicarbonitrile (4bg): According to procedure
B, cyclopentene 4bg was obtained from allene 1b (19.4 mg,
0.1 mmol), malononitrile derivative 2g (30.6 mg, 0.15 mmol),
n-Bu4NBr (3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg,
0.01 mmol) in THF (1 mL). Column chromatography with
Trans-(Æ)-5-methyl-2-phenyl-4-(phenylsulfonyl)cyclopent-2-
53 ene-1,1-dicarbonitrile (4ba): According to procedure B,
cyclopentene 4ba was obtained from allene 1b (19.4 mg,
0.1 mmol), malononitrile derivative 2a (23.1 mg, 0.15 mmol),
n-Bu4NBr (3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg,
0.01 mmol) in THF (1 mL). Yield 77% (26.8 mg,
54
55
56
57
pentane/AcOEt/CH2Cl2 =8/1/1.
Yield
73%
(29.1 mg,
0.073 mmol). The product was obtained as a single diaster-
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8
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1
eoisomer (dr > 99:1). White solid, mp: 171–1728C. H NMR
chromatography with pentane/AcOEt/CH2Cl2 =7/1.5/1.5.
1
2
3
4
5
6
7
8
9
3
(400 MHz, CDCl3): d 1.60 (d, J=7.0, 3H), 3.45 (quintapp, J=
Yield 89% (31 mg, 0.089 mmol). White solid, mp: 171–
3
3
1
7.2, 1H), 4.29 (dd, J=2.2 and 7.6, 1H), 6.43 (d, J=2.2, 1H),
7.54–7.60 (m, 3H), 7.65–7.69 (m, 2H), 7.74–7.78 (m, 1H),
7.84–7.93 (m, 3H), 7.97–8.00 (m, 2H), 8.05–8.07 (m, 1H). 13C
NMR (100 MHz, CDCl3): d 16.3, 46.0, 47.0, 75.3, 112.2, 113.9,
123.3, 126.3, 126.6, 126.8, 127.2, 127.8, 127.9, 128.9, 129.0
(2C), 129.3, 129.9 (2C), 132.9, 133.9, 135.0, 136.4, 142.1. IR
(neat, ATR probe, cmÀ1): 2442, 2159, 1976, 1446, 1308, 1211,
1140, 1084, 860, 801. HRMS (ESI): Calculated for
C24H18N2O2SNa [(M+Na)+]: 421.0987, found: 421.0983.
1728C. H NMR (400 MHz, CDCl3): d 2.05 (s, 3H), 2.98 and
3.04 (AB part of ABX system, 2JAB =15.2, 3JAX =5.2 and
3JBX =8.5, 1H each), 4.49–4.54 (m, 1H), 7.29–7.32 (m, 2H),
7.44–7.48 (m, 3H), 7.66–7.70 (m, 2H), 7.76–7.81 (m, 1H),
7.94–7.97 (m, 2H). 13C NMR (100 MHz, CDCl3): d 15.7, 37.6,
42.6, 72.8, 113.3, 114.8, 128.7 (2C), 129.0 (2C), 129.2 (2C),
129.89, 129.94 (2C), 130.5, 135.1, 136.2, 137.1, 139.0. IR (neat,
ATR probe, cmÀ1): 2925, 1445, 1316, 1306, 1148, 1085, 1070,
768, 753, 726. HRMS (ESI): Calculated for C20H16N2O2SNa
[(M+Na)+]: 371.0830, found: 371.0844.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
Trans-(Æ)-5-methyl-4-(phenylsulfonyl)-2-(2-thienyl)-cyclo-
pent-2-ene-1,1-dicarbonitrile (4bj): According to procedure
B, cyclopentene 4bj was obtained from allene 1b (19.4 mg,
0.1 mmol), malononitrile derivative 2j (24 mg, 0.15 mmol),
n-Bu4NBr (3.3 mg, 0.01 mmol) and PhSO2Na (1.8 mg,
0.01 mmol) in THF (1 mL). Column chromatography with
pentane/AcOEt/CH2Cl2 =7.5/1.25/1.25. Yield 49% (17.5 mg,
0.049 mmol). The product was obtained as a single diaster-
2-(4-Methoxyphenyl)-3-methyl-4-(phenylsulfonyl)cyclopent-
3-ene-1,1-dicarbonitrile (3cc): Cyclopentene 3cc was ob-
tained from allene 1c (19.4 mg, 0.1 mmol), malononitrile
derivative 2c (27.6 mg, 0.15 mmol), n-Bu4NBr (3.3 mg,
0.01 mmol) and PhSO2Na (1.8 mg, 0.01 mmol) in THF
(1 mL). Column chromatography with pentane/AcOEt/
CH2Cl2 =8/1/1. Yield 78% (29.3 mg, 0.078 mmol). Yellow
1
1
eoisomer (dr>99:1). Pink solid, mp: 197–1988C. H NMR
solid, mp: 58–598C. H NMR (400 MHz, CDCl3): d 2.15 (s,
3
(400 MHz, CDCl3): d 1.55 (d, J=7.1, 3H), 3.38 (quint, J=
7.1, 1H), 4.21 (dd, J=2.4 and 6.9, 1H), 6.15 (d, J=2.4, 1H),
3H), 3.34–3.45 (m, 2H), 3.81 (s, 3H), 4.39 (s, 1H), 6.90–6.92
(m, 2H), 6.99–7.02 (m, 2H), 7.63–7.67 (m, 2H), 7.72–7.76 (m,
1H), 7.95–7.97 (m, 2H). 13C NMR (100 MHz, CDCl3): d 14.4,
38.4, 43.3, 55.4, 65.8, 113.0, 115.1 (2C), 115.7, 123.4, 127.4
(2C), 129.8 (2C), 129.9 (2C), 133.4, 134.4, 139.5, 151.8, 160.8.
IR (neat, ATR probe, cmÀ1): 2925, 1640, 1446, 1321, 1306,
1149, 1093, 752, 725, 687. HRMS (ESI): Calculated for
C21H18N2O3SNa [(M+Na)+]: 401.0936, found: 401.0937.
3
3
3
3
7.10 (dd, J=3.8 and 5.0, 1H), 7.42 (d, J=5.0, 1H), 7.45 (d,
3J=3.8, 1H), 7.63–7.67 (m, 2H), 7.73–7.77 (m, 1H), 7.92–7.94
(m, 2H). 13C NMR (100 MHz, CDCl3): d 16.8, 45.4, 47.2, 75.8,
111.7, 113.6, 123.9, 127.8, 128.4, 128.6, 129.0 (2C), 129.9 (2C),
132.5, 135.0, 135.8, 136.0. IR (neat, ATR probe, cmÀ1): 2447,
2160, 2030, 1977, 1582, 1446, 1309, 1221, 1142, 1084. HRMS
(ESI): Calculated for C18H14N2O2S2Na [(M+Na)+]:
377.0394, found: 377.0393.
3-Methyl-4-(phenylsulfonyl)-2-(2-thienyl)-cyclopent-2-ene-
1,1-dicarbonitrile (4cj): Cyclopentene 4cj was obtained from
allene 1c (19.4 mg, 0.1 mmol), malononitrile derivative 2j
(24 mg, 0.15 mmol), n-Bu4NBr (3.3 mg, 0.01 mmol) and
PhSO2Na (1.8 mg, 0.01 mmol) in THF (1 mL). Column
chromatography with pentane/AcOEt/CH2Cl2 =7/1.5/1.5.
Yield 82% (29.2 mg, 0.082 mmol). White solid, mp: 166–
Typical Procedure for (3+2) Annulations with Allenyl
Sulfone 1c: Allenyl sulfone 1c (1 equiv.), Michael acceptor 2
(1.5 equiv.), n-Bu4NBr (10 mol%) were diluted in THF
(0.1 M) and PhSO2Na (10 mol%) was added. After stirring
at room temperature for 16 hours, the reaction mixture was
concentrated under reduced pressure and directly purified by
column chromatography on silica gel to afford the pure
cyclopentenes 3 or 4.
1
1678C. H NMR (400 MHz, CDCl3): d 2.31 (br s, 3H), 3.03
2
3
and 3.08 (AB part of ABX system, JAB =15.4, JAX =4.7 and
3
3JBX =8.6, 1H each), 4.05–4.53 (m, 1H), 7.16 (dd, J=3.8 and
3
4
5.1, 1H), 7.40–7.42 (m, 1H), 7.52 (dd, J=5.1 and J=0.9,
1H), 7.62–7.66 (m, 2H), 7.73–7.76 (m, 1H), 7.90–7.92 (m,
2H). 13C NMR (100 MHz, CDCl3): d 16.7, 37.3, 41.9, 73.9,
113.4, 115.1, 127.7, 128.8, 128.9, 129.0 (2C), 130.0 (2C), 130.4,
131.6, 135.1, 135.9, 137.2. IR (neat, ATR probe, cmÀ1): 2502,
2160, 2029, 1977, 1443, 1313, 1306, 1146, 1085, 813. HRMS
(ESI): Calculated for C18H14N2O2S2Na [(M+Na)+]:
377.0394, found: 377.0392.
3-Methyl-2-phenyl-4-(phenylsulfonyl)cyclopent-3-ene-1,1-di-
carbonitrile (3ca): Cyclopentene 3ca was obtained from
allene 1c (19.4 mg, 0.1 mmol), malononitrile derivative 2a
(23.1 mg, 0.15 mmol), n-Bu4NBr (3.3 mg, 0.01mmol) and
PhSO2Na (1.8 mg, 0.01 mmol) in THF (1 mL). Column
chromatography with pentane/AcOEt/CH2Cl2 =8/1/1. Yield
1
85% (29.6 mg, 0.085 mmol). White solid, mp: 128–1298C. H
NMR (400 MHz, CDCl3): d 2.16 (s, 3H), 3.36–3.48 (m, 2H),
4.43 (s, 1H), 7.07–7.10 (m, 2H), 7.39–7.46 (m, 3H), 7.63–7.68
46 (m, 2H), 7.72–7.77 (m, 1H), 7.95–7.98 (m, 2H). 13C NMR
Chemical Transformations of Cyclopentene 4aa
(100 MHz, CDCl3): d 14.5, 38.3, 43.5, 66.3, 112.8, 115.6, 127.4
(2C), 128.6 (2C), 129.75 (2C), 129.83 (2C), 130.2, 131.7,
133.9, 134.5, 139.5, 151.4. IR (neat, ATR probe, cmÀ1): 2925,
1640, 1446, 1321, 1306, 1149, 1093, 752, 725, 687. HRMS
(ESI): Calculated for C20H16N2O2SNa [(M+Na)+]: 371.0830,
found: 371.0822.
47
48
49
50
51
52
1-Phenyl-4-(phenylsulfonyl)-6-oxabicyclo[3.1.0]hexane-2,2-
dicarbonitrile (8): To a solution of cyclopentene 4aa (80 mg,
0.24 mmol, 1 equiv.) in dry CH2Cl2, NaHCO3 (60 mg,
0.72 mmol, 3 equiv.) and 3-chloroperbenzoic acid (m-CPBA
70%, 177 mg, 0.72 mmol, 3 equiv.) were added. After stirring
the reaction mixture at room temperature for 48 hours, the
volatiles were removed under reduced pressure. The crude
product was then purified by column chromatography
(pentane/AcOEt=4/1) on silica gel to afford the pure
epoxide 8 as a single diastereoisomer (dr>99:1). Yield 84%
53 3-Methyl-2-phenyl-4-(phenylsulfonyl)cyclopent-2-ene-1,1-di-
carbonitrile (4ca): Cyclopentene 4ca was obtained from
allene 1c (19.4 mg, 0.1 mmol), malononitrile derivative 2a
(23.1 mg, 0.15 mmol), n-Bu4NOAc (3 mg, 0.01 mmol) and
PhSO2Na (1.8 mg, 0.01 mmol) in THF (1 mL). Column
54
55
56
57
1
(71 mg, 0.20 mmol). White solid, mp: 193–1948C. H NMR
Adv. Synth. Catal. 2018, 360, 1–12
9
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COMMUNICATIONS
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(600 MHz, CDCl3): d 2.67 (dd, 2J=15.6 and 3J=8.8, 1H),
[2] C. Gomez, J.-F. Betzer, A. Voituriez, A. Marinetti,
1
2
3
4
5
6
7
8
9
2
3
3.14 (dapp, J=15.6, 1H), 4.08 (sapp, 1H), 4.08 (dapp, J=8.8,
1H), 7.49–7.53 (m, 3H), 7.67–7.70 (m, 2H), 7.73–7.75 (m,
2H), 7.77–7-80 (m, 1H), 8.02–8.04 (m, 2H). 13C NMR
(125 MHz, CDCl3): d 35.8, 40.4, 63.7 (2C), 71.0, 112.3, 113.1,
128.2, 128.6, 128.9, 129.1, 130.3, 131.0, 135.4, 136.8. IR (neat,
ATR probe, cmÀ1): 2924, 1310, 1151, 747, 727, 696, 591, 564,
547, 513. HRMS (ESI): Calculated for C19H14N2O3SNa [(M+
Na)+]: 373.0623, found: 373.0622.
ChemCatChem 2013, 5, 1055.
[3] An original feature of the catalytic cycle is that the
expelled sulfinate originates from the starting allenyl
sulfone. This characteristic implies the use of identical
sulfur motifs within the allene and the sulfinate salt.
[4] For intermolecular versions: a) A. Padwa, P. E. Yeske, J.
Am. Chem. Soc. 1988, 110, 1617; b) A. Padwa, P. E.
Yeske, J. Org. Chem. 1991, 56, 6386.
[5] For intramolecular versions: a) A. Padwa, S. H. Watter-
son, Z. Ni, J. Org. Chem. 1994, 59, 3256; b) A. Padwa,
S. S. Murphree, Z. Ni, S. H. Watterson, J. Org. Chem.
1996, 61, 3829; c) A. Padwa, H. Lipka, S. H. Watterson,
S. S. Murphree, J. Org. Chem. 2003, 68, 6238.
[6] A. NfflÇez, M. Rosario Martín, A. Fraile, J. L. García
Ruano, Chem. Eur. J. 2010, 16, 5443.
[7] a) J. T. Flasz, K. J. Hale, Org. Lett. 2012, 14, 3024; b) Z.
Xiong, K. J. Hale, Org. Lett. 2016, 18, 4254.
[8] For related intermolecular extensions leading to 3-
pyrrolines and chromans, see: a) E. Moreno-Clavijo,
A. T. Carmona, H.-U. Reissig, A. J. Moreno-Vargas, E.
Alvarez, I. Robina, Org. Lett. 2009, 11, 4778; b) F. Hu,
X. Guan, M. Shi, Tetrahedron 2012, 68, 4782.
[9] T. Martzel, J.-F. Lohier, A.-C. Gaumont, J.-F. Bri›re, S.
Perrio, Adv. Synth. Catal. 2017, 359, 96.
[10] For a review dedicated to a,a-dicyano olefins: J. Kaur,
P. Chauhan, S. S. Chimni, Org. Biomol. Chem. 2016, 14,
7832.
[11] For reviews, see: a) S. Shirakawa, K. Maruoka, Angew.
Chem. Int. Ed. 2013, 52, 4312. Angew. Chem. 2013, 125,
4408; b) J. Tan, N. Yasuda, Org. Proc. Res. Dev. 2015,
19, 1731; c) J. Schçrgenhumer, M. Tiffner, M. Waser,
Beilstein J. Org. Chem. 2017, 13, 1753; d) S. Oudeyer, V.
Levacher, J.-F. Bri›re, Chiral Quaternary Ammonium
Salts in Organocatalysis, in Radical and Ion-pairing
Strategies in Asymmetric Organocatalysis, Chapter 2,
ISTE Press and Elsevier, 2017, pp. 87.
[12] See ref. 6 for the beneficial use of PT conditions
through the introduction of ammonium salts or crown
ethers.
[13] In a Special Issue of Heterocycles journal: S. Kuwano, T.
Masuda, K. Yamaguchi, T. Arai, Heterocycles 2017, 95,
232.
[14] A retrosynthetic disconnection indicated that 5 might
be produced from two molecules of 1a and a single
molecule of 2a (see Supporting Information).
[15] D. Blanco-Ania, C. Valderas-Cortina, P. H. H. Herm-
kens, L. A. J. M. Sliedregt, H. W. Scheeren, F. P. J. T.
Rutjes, Molecules 2010, 15, 2269.
1-Cyano-2-phenyl-4-(phenylsulfonyl)cyclopent-2-enecarbox-
ylic Acid Methyl Ester (9): To a solution of cyclopentene 4aa
(54 mg, 0.16 mmol, 1 equiv.) in methanol, K2CO3 (110 mg,
0.80 mmol, 5 equiv.) was added. After stirring the reaction
mixture at room temperature for 16 hours, the solvent was
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
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53
54
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1
removed under reduced pressure. H NMR analysis of the
crude product indicated the formation of the two diaster-
eoisomers of 9 in a 68:32 ratio. Separation of both products
was readily achieved through purification by column chro-
matography (toluene/AcOEt=15/1) on silica gel.
Major diastereoisomer (1S*,4S*)-9: Yield 48% (27.9 mg,
0,075 mmol). White solid, mp: 125–1268C. 1H NMR
3
(500 MHz, CDCl3): d 2.99 (d, J=7.2, 2H), 3.77 (s, 3H), 4.68
3
3
(dt, J=2.4 and 7.2, 1H), 6.39 (d, J=2.4, 1H), 7.36–7.38 (m,
3
3
3H), 7.44–7.46 (m, 2H), 7.61 (t, J=7.8, 2H), 7.71 (t, J=7.5,
1H), 7.93 (d, J=7.5, 2H). 13C NMR (125 MHz, CDCl3): d
3
37.5, 54.3, 54.5, 70.7, 117.2, 125.9, 126.7, 129.1, 129.2, 129.8,
130.0, 131.0, 134.8, 136.3, 145.6, 168.4. IR (neat, ATR probe,
cmÀ1): 2887, 1739, 1285, 1198, 1133, 1081, 752, 719, 690, 650,
578, 511. HRMS (ESI): Calculated for C20H17NO4SNa [(M+
Na)+]: 390.0776, found: 390.0777.
Minor diastereoisomer (1S*,4R*)-9: Yield 22% (13.12 mg,
0,035 mmol). White solid, mp: 129–1308C. 1H NMR
(500 MHz, CDCl3): d 3.02 (AB part of ABX system 2J=14.2,
3J=7.5 and 8.0, 1H each), 3.66 (s, 3H), 4.70 (dtapp, 3J=2.2 and
3
7.7, 1H), 6.33 (d, J=2.2, 1H), 7.35–7.37 (m, 3H), 7.43–7.45
3
3
(m, 2H), 7.63 (t, J=7.8, 2H), 7.72 (t, J=7.5, 1H), 7.94 (d,
3J=7.5, 2H). 13C NMR (125 MHz, CDCl3): d 37.6, 54.3, 54.6,
70.0, 117.9, 125.7, 126.6, 129.0, 129.1, 129.7, 129.9, 131.3,
134.6, 136.9, 145.7, 167.3. IR (neat, ATR probe, cmÀ1): 3078,
1759, 1290, 1207, 1137, 1081, 687, 644, 581, 539. HRMS
(ESI): Calculated for C20H17NO4SNa [(M+Na)+]: 390.0776,
found: 390.0777.
Acknowledgements
We acknowledge financial support from Region Normandie
(CRUNCh network), CNRS, EFRD and Labex SynOrg
(ANR-11-LABX-0029). This work has been also partially
supported by INSA Rouen, ENSICAEN, University of Rouen
and Caen Normandy.
[16] a) P. Beak, D. A. Burg, J. Org. Chem. 1989, 54, 1647;
b) V. Gembus, S. Postikova, V. Levacher, J.-F. Bri›re, J.
Org. Chem. 2011, 76, 4194.
[17] For a recent phosphine-catalyzed (4+1) annulation
with allenoates, in which a rapid proton transfer/double-
bond migration reaction was observed: K. Zielke, M.
Waser, Org. Lett. 2018, 20, 768.
[18] O. Lahtigui, F. Emmetiere, W. Zhang, L. Jirmo, S.
Toledo-Roy, J. C. Hershberger, J. M. Macho, A. J. Gren-
ning, Angew. Chem. Int. Ed. 2016, 55, 15792; Angew.
Chem. 2016, 128, 16024.
References
[1] a) Y. Wei, M. Shi, Org. Chem. Front. 2017, 4, 1876; b) T.
Wang, X. Han, F. Zhong, W. Yao, Y. Lu, Acc. Chem.
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Soc. Rev. 2014, 43, 2927.
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[19] A. Vlasceanu, B. N. Frandsen, A. B. Skov, A. S. Hansen,
M. G. Rasmussen, H. G. Kjaergaard, K. V. Mikkelsen,
M. B. Nielsen, J. Org. Chem. 2017, 82, 10398.
[20] See Supporting Information for some results with
commercially available chiral catalysts in THF solution
with allenyl sulfones 1a and 1b.
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Sulfinate-Organocatalyzed (3+2) Annulation of Allenyl
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Quaternary Ammonium Phase Transfer Agent
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