Probing phosphane-mediated [2+1] annulation reactions

Article abstract of DOI:10.1002/ejoc.200901235

Phosphane-mediated cyclizations between a-keto nitriles and methylidenemalononitriles, producing highly functionalized cyclopropanes in good to excellent yields, are re-ported. The presence of strongly electron-withdrawing cyano groups directly bound to the ketone carbonyl groups is believed to play a critical role in these transformations.

Full text of DOI:10.1002/ejoc.200901235

FULL PAPER
DOI: 10.1002/ejoc.200901235
Probing Phosphane-Mediated [2+1] Annulation Reactions
Xu-Guang Liu,[a] Yin Wei,*[b] and Min Shi*[a,b]
Keywords: Cyclization / Phosphanes / Cyclopropanes / Annulation
Phosphane-mediated cyclizations between α-keto nitriles
and methylidenemalononitriles, producing highly function-
ported. The presence of strongly electron-withdrawing cyano
groups directly bound to the ketone carbonyl groups is be-
alized cyclopropanes in good to excellent yields, are re- lieved to play a critical role in these transformations.
ionic intermediate then undergoing addition to the carbonyl
Introduction
group of the 4- or 2-nitrobenzaldehyde to form another
Organophosphorus compounds are widely used in or-
zwitterionic intermediate, which subsequently undergoes
ganic synthesis; examples include the use of phosphonium
cyclization to give an intermediate and then decomposes
ylides in the Wittig reaction,[1] the use of phosphanes in
to generate the products with elimination of phosphate or
the Staudinger reaction,[2] the Mitsunobu reaction,[3] and
transition-metal-catalyzed reactions in which phosphanes
act as ligands. Recently they have become frequently used
as organocatalysts or reagents because their “soft” nucleo-
philicity is one of the most important characteristic features
for the facilitation of many types of reactions including the
Morita–Baylis–Hillman reaction,[4] the Rauhut–Currier re-
action,[5] the Stetter reaction,[6] the Michael addition,[7]
isomerization of C–C multiple bonds,[8] alcohol acylation
and kinetic resolution,[9] nucleophilic addition to the α- and
γ-positions of activated alkynes and allenes,[10] ring open-
ing,[11] and reduction of activated carbonyl groups.[12] Nu-
cleophilic phosphane catalysts especially have emerged as
efficient means to generate carbo- and heterocycles.[13] In
particular, Lu’s phosphane-catalyzed [3+2] cycloadditions
to form cyclopentenes from allenoates and alkenes have
been applied in the synthesis of several natural products.[14]
Additionally, Kwon has reported phosphane-catalyzed
[4+2] annulations for the synthesis of tetrahydropyridines
and cyclohexenes.[15]
phosphane oxide.[16] Unfortunately, the substrate is strictly
limited to 4- or 2-nitrobenzaldehyde; when other aldehydes
were used, there was no reaction at all. We hypothesize that
less electrophilic substrates experience difficulty in under-
going addition of the zwitterionic nucleophile generated
from the phosphane and the methylidenemalononitrile, per-
haps similarly to the case of the phosphane-mediated re-
duction of activated carbonyl compounds.[12] We therefore
envisioned that the use of activated carbonyl compounds
incorporating strongly electron-withdrawing groups, such
as 2,2,2-trifluoro-1-arylethan-1-one, α-keto esters, and α-
keto nitriles, may lead to the occurrence of various kinds of
nucleophilic additions.[17] In this paper we explore phos-
phane-mediated [2+1] annulation reactions between α-keto
nitriles and various electrophiles. Through these phos-
phane-mediated annulation reactions (Scheme 1), multiply
functionalized cyclopropanes were obtained in good to ex-
cellent yields and with moderate diastereoselectivities. Sur-
prisingly, an unexpected rearrangement was found during
the investigation of phosphane-mediated reactions between
α-keto nitriles and imines.
We have very recently reported a phosphane(phosphite)-
mediated method for the formation of cyclopropanes and
aziridines from 4- or 2-nitrobenzaldehyde and methylidene-
malononitriles.[16] The proposed mechanism includes the
formation of a zwitterionic intermediate from the phos-
phane and the methylidenemalononitrile, with the zwitter-
[a] Laboratory for Advanced Materials and Institute of Fine
Chemicals, East China University of Science & Technology,
130 Mei Long Road, Shanghai 200237, P. R. of China
Fax: +86-21-64166128
Scheme 1. Phosphane-mediated [2+1] annulation.
[b] State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Lu, Shanghai 200032, P. R. of China
E-mail: Mshi@mail.sioc.ac.cn
Results and Discussion
weiyin@mail.sioc.ac.cn
We initially examined the reaction between 4-chloro-
benzonitrile (1a, Table 1) and 2-benzylidenemalononitrile
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.200901235.
Eur. J. Org. Chem. 2010, 1977–1988
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1977

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
Table 1. Phosphane(phosphite)-mediated reaction between 4-chlorobenzonitrile (1a) and 2-benzylidenemalononitrile (2a).[a]
[a] Reactions were carried out with 4-chlorobenzonitrile (1a, 0.3 mmol), 2-benzylidenemalononitrile (2a, 0.3 mmol), and PR3 (0.3 mmol)
in THF (2.0 mL) at reflux. [b] Yield of isolated product and then the ratio between the isolated products 3a and 3aЈ. [c] No reaction.
[d] The reaction was carried out at room temperature. [e] The product ethyl 4-chlorobenzoate was isolated in the reaction (yield 68%).
[f] Complex products.
(2a) in the presence of P(OEt)3 (1.0 equiv.) in tetra-
Other electron-deficient carbonyl compounds, however,
hydrofuran (THF) at reflux, the optimal conditions for our such as 2,2,2-trifluoro-1-arylethan-1-ones [ArC(O)CF3] and
previous cyclopropane synthesis.[16] To our delight, the re- α-keto esters [ArC(O)CO2Et], were not suitable for this re-
action proceeded smoothly and two products were ob- action under the same conditions. This observation indi-
tained. One of the products was assigned as the cyclopro- cates that the presence of a very strongly electron-with-
pane 3aЈ and confirmed by X-ray diffraction (Figure 1),[18] drawing substituent directly bound to the ketone carbonyl
and the other product was assigned as 3a, the isomer of group is essential to facilitate the reaction, which is similar
3aЈ.
to what we have previously found in the phosphane(phos-
phite)-mediated reactions of 4- or 2-nitrobenzaldehyde and
methylidenemalononitriles.[16]
We next examined the reaction between 4-chlorobenzoni-
trile (1a) and 2-benzylidenemalononitrile (2a) in the pres-
ence of a variety of phosphanes or phosphites in tetra-
hydrofuran (THF) at reflux in order to identify the best
promoter. The results are summarized in Table 1. As can be
seen, no reaction had occurred after 24 h (Table 1, Entry 1)
with use of the less nucleophilic PPh3 as the promoter. Use
of phosphanes of increasing nucleophilicity led to increased
yields. With Ph2PMe as the promoter only trace of products
could be obtained after 10 h (Table 1, Entry 2), whereas
with PhPMe2 as the promoter the yield of 3a and 3aЈ could
be improved to 73% (Table 1, Entry 3). In particular, with
the strongly nucleophilic phosphane PBu3 as the promoter
(Table 1, Entry 4) the reaction proceeded smoothly to give
the annulation products 3a and 3aЈ in 91% yield in a short
reaction time (only 1.0 h), although the diastereoselectivity
was not very good. Variation of reaction temperature and
reaction time revealed that a reasonable yield could still be
Figure 1. The single-crystal X-ray structure of 3aЈ.
1978
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Probing Phosphane-Mediated [2+1] Annulation Reactions
obtained if the reaction temperature was lowered to room but P(OPh)3 was ineffective for the formation of cyclopro-
temperature and the reaction time was prolonged to 2.0 h panes 3a and 3aЈ (Table 1, Entry 7). Solvent screening
(Table 1, Entry 6). Selected phosphites – Ph2POMe and showed that THF was the best solvent (Table 1, Entries 9–
P(OEt)3 – were also able to promote this reaction, giving 12). The best reaction conditions are thus with PBu3 as the
moderate yields of the product (Table 1, Entries 5 and 8), promoter in THF at reflux.
Table 2. Phosphane-mediated annulation reactions: synthesis of multiply substituted cyclopropanes.[a]
[a] Reactions were carried out with acyl cyanides 1 (0.3 mmol), arylmethylidenemalononitriles 2 (0.3 mmol), and PBu3 (0.3 mmol) in
THF (2.0 mL) at reflux. [b] Yield of isolated product (total yields of the two isomers). [c] The ratio was determined between the two
isolated products 3 (CN and R2 trans) and 3’ (CN and R2 cis). [d] The ratio of 3j to 3jЈ was measured by 1H NMR of the crude products,
complete separation of the two isomers from one another being difficult. [e] Difficult to determine from the 1H NMR spectroscopic data
and the products cannot be distinguished from one another. [f] Complex products, not characterized.
Eur. J. Org. Chem. 2010, 1977–1988
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1979

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
With these optimized reaction conditions to hand, we actions arose. Replacement of the two cyano groups in the
next turned our attention to the generality of the reaction. substrates 2 by two ester groups did not result in the forma-
A variety of (arylmethylidene)malononitriles 2 were exam- tion of the desired products under the optimized reaction
ined under these optimal conditions and the results are conditions. Replacement of just one cyano group in a sub-
shown in Table 2. The reactions proceeded smoothly to pro- strate 2 by an ester group, however, did result in the desired
duce the multiply functionalized cyclopropanes 3 as mix- products 5 being obtained in moderate yields, which indi-
tures of two diastereoisomers and in good to excellent cates that at least one of the strongly electron-withdrawing
yields with respect to the various substituted (arylmethylid- cyano groups in each of the substrates 2 is essential for this
ene)malononitriles 2, except in the case of substrate 2e, with reaction. It should be noted that only two diastereomers
two substitutes at the ortho- and meta-positions of its ben- of the four possible diastereomers could be obtained. The
zene ring, which afforded 3e in only 48% yield, although structures of these isolated cyclopropane products 5a and
with the best diastereoselectivity (Table 2, Entry 5). Presum- 5aЈ were fully characterized spectroscopically (see the Sup-
ably the steric hindrance of the two substituents at the porting Information). The diastereochemical outcome with
ortho- and meta-positions in the benzene ring leads both to regard to compounds 5 was ascertained by single-crystal X-
the poor yield and the high diastereoselectivity. Notably, ray diffraction analyses of 5a and 5cЈ (an analogue of 5aЈ).
with 2-(naphthalen-1-ylmethylene)malononitrile (2h) and Their ORTEP drawings are shown in Figures 2[18] and 3[18]
nicotinonitrile 2i, the corresponding cyclopropanes were and their CIF data are presented in the Supporting Infor-
obtained in good yields (Table 2, Entries 8 and 9). More- mation.
over, aliphatic methylidenemalononitriles also exhibited
good reactivities for these reactions, with good to moderate
yields (Table 2, Entries 10 and 11).
A variety of acyl cyanides 1 were further examined under
the optimized reaction conditions, and these results are also
included in Table 2. As shown, variation of the substituent
in 1 did not affect the yields of the corresponding products
3 in any instance, with the cyclopropanes 3l–3t being ob-
tained in good to excellent yields (Table 2, Entries 12–19).
In addition, 1-naphthoyl cyanide was also able to react with
the arylmethylidenemalononitrile 2a, giving the cyclo-
propane 3t in 55% yield (Table 2, Entry 20). Use of an
alkyl-substituted cyanide (compound 1h) as the substrate,
however, provided complex product mixtures (Table 2, En-
try 21).
The scope and limitations of this reaction still remained
unclear at this stage. The question of whether the strongly
Figure 3. X-ray crystal structure of 5cЈ.
electron-withdrawing dicyano groups in the substrates 2
were essential for these phosphane-mediated annulation re-
We next examined the scope of the phosphane-mediated
reactions between the acyl cyanides 1 and a series of sub-
strates 4 under the optimized reaction conditions; the re-
sults are summarized in Table 3. The reactions were found
to be general with respect to a variety of substituted com-
pounds 1 and 4 bearing electron-withdrawing (Table 3, En-
tries 1–3), electron-donating (Table 3, Entries 4 and 6),
naphthyl (Table 3, Entry 9), and heteroaromatic (Table 3,
Entries 7 and 8) substituents. It should be noted that the
ratio of the products 5 and 5Ј is almost 1:1 in each case,
but that in most cases the two diastereoisomers could easily
be separated by flash column chromatography.
A possible mechanism for these reactions, based on a
previously proposed mechanism,[16] is suggested in
Scheme 2. The first step is the formation of the zwitterionic
intermediate A from the phosphane and the arylmethylid-
enemalononitrile. We presume that the strongly electro-
philic carbonyl compound undergoes addition of the zwit-
terionic nucleophile more easily to make the intermediate
B, which facilitates the following cyclization and subsequent
decomposition with elimination of phosphane oxide and
formation of the product 3.
Figure 2. X-ray crystal structure of 5a.
1980
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Probing Phosphane-Mediated [2+1] Annulation Reactions
Table 3. Phosphane-mediated [2+1] annulation reactions of 1 and 4.[a]
[a] Reactions were carried out with acyl cyanides 1 (0.3 mmol), 4 (0.3 mmol), and tributylphosphane (0.3 mmol) in THF (2.0 mL) at
reflux. [b] Yield of the isolated product (total yields of the two isomers). [c] The ratio was determined between the two isolated products
5 and 5Ј.
Surprisingly, the expected aziridine 7 was not formed. The
reaction instead afforded a product that was subsequently
characterized as the structure 8 (Scheme 3, 38% yield). The
structure 8 was assigned on the basis of spectroscopic
analysis and was subsequently confirmed unequivocally by
single X-ray analysis (Figure 4).[18]
From the X-ray crystal structure of product 8 we can see
that the tosyl group had migrated from the nitrogen atom
to the carbon atom. We have recently observed and re-
ported similar migrations in reactions between acyl cya-
nides and “Huisgen zwitterion”, which included formal mi-
grations from a nitrogen atom to a carboxyl group oxygen
atom.[19]
Although the mechanistic underpinnings of the reaction
are not precisely known, the following explanation for the
formation of product 8 may be advanced. Presumably, the
Scheme 2. A plausible reaction mechanism.
intermediate A (Scheme 4) formed from the phosphane and
N-tosylbenzaldimine undergoes nucleophilic addition to the
Having established phosphane-mediated [2+1] annu- acyl cyanide, activated by the cyano group, resulting in in-
lations between α-keto nitriles and methylidenemalononitr- termediate B. Intermediate B undergoes cyclization and
ile for the synthesis of cyclopropanes, we reasoned that it subsequently decomposes with loss of phosphane oxide to
might also be possible to formulate a nitrogen-containing generate compound C, containing the aziridine ring. The
heterocycle through a phosphane-mediated annulation re- three-membered ring in C is very unstable, due to high
action of this type if α-keto nitriles and imines were em- strain energy, and it is easily reopened to give the later inter-
ployed.[16] We initially examined this type of reaction with mediate D. Intermediate D rearranges to the product 8
the acyl cyanide 1b and the N-tosylbenzaldimine 6 in the through a nitrogen-to-carbon migration of the tosyl group
presence of a stoichiometric amount of tributylphosphane. (Scheme 4).
Eur. J. Org. Chem. 2010, 1977–1988
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1981

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
Scheme 3. The reaction between the acyl cyanide 1b and the N-tosylbenzaldimine 6.
Scheme 4. Possible pathway for the formation of 8.
synthesis is general with respect to various substrates con-
taining carbonitrile, aryl, and ester functional groups. In
addition, an interesting rearrangement was found in phos-
phane-mediated reactions between acyl cyanides and im-
ines. Further efforts will focus on expanding the versatility
of these new [2+1] annulations and on elucidation of fur-
ther mechanistic details of these reactions.
Experimental Section
General Remarks: Melting points were determined with a digital
1
melting point apparatus. H and 13C NMR spectra were recorded
at 300 (400) and 75 (100) MHz, respectively. Mass and HRMS
spectra were recorded by EI methods. Organic solvents were dried
by standard methods if necessary. Satisfactory CHN microanalyses
were obtained with an analyzer. Commercially available reagents
were used without further purification. All reactions were moni-
tored by TLC with silica gel coated plates. Flash column
chromatography was carried out with silica gel at increased pres-
sure.
Figure 4. X-ray crystal structure of 8.
In conclusion, we have developed a quite simple and ef-
ficient protocol for the synthesis of multiply substituted
cyclopropanes through a novel phosphane-mediated [2+1]
annulation process, which furnishes the multiply substituted
cyclopropanes in moderate to excellent yields under mild
reaction conditions, with use only of simple and cheap
Typical Reaction Procedure for the Phosphane-Mediated [2+1] An-
nulation: A phosphane (0.3 mmol) was added under argon to a
mixture of an acyl cyanide 1 (0.3 mmol) and an arylmethylidenem-
alononitrile 2 (0.3 mmol) in solvent and the reaction mixture was
stirred at reflux for the required time as indicated in the tables.
starting materials and promoters. Moreover, the presented After the reaction solution had been concentrated under reduced
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Probing Phosphane-Mediated [2+1] Annulation Reactions
pressure, the residue was purified by flash chromatography on silica
gel (eluent: EtOAc/petroleum ether 1:15–1:8) to afford the pure
product 3.
1568, 1496, 1478, 1097 cm–1. MS (EI): m/z = 385 (8.43) [M + 4]+,
384 (7.75) [M + 3]+, 383 (35.58) [M + 2]+, 382 (9.09) [M + 1]+, 381
(26.45) [M]+. C18H9BrClN3 (380.9668): calcd. C 56.50, H 2.37, Br
20.88, Cl 9.27, N 10.98; found C 56.61, H 2.29, N 10.94.
(2R,3S)-2-(4-Chlorophenyl)-3-phenylcyclopropane-1,1,2-tricarboni-
1
trile (3a): M.p. 213–214 °C. H NMR (CDCl3, 300 MHz, TMS): δ
(2R,3S)-3-(2-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2-
tricarbonitrile (3d): M.p. 212–214 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 3.87 (s, 1 H, CH), 7.43 (t, J = 7.6 Hz, 1 H, Ar), 7.51 (t,
J = 7.6 Hz, 1 H, Ar), 7.55 (d, J = 8.8 Hz, 2 H, Ar), 7.59 (d, J =
8.8 Hz, 2 H, Ar), 7.70 (d, J = 7.6 Hz, 1 H, Ar), 7.80 (d, J = 7.6 Hz,
1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 22.3, 37.3, 40.9,
109.5, 110.5, 113.5, 125.4, 126.4, 127.1, 128.4, 130.0, 130.4, 132.1,
= 3.91 (s, 1 H, CH), 7.05 (d, J = 7.5 Hz, 2 H, Ar), 7.23 (d, J =
7.5 Hz, 2 H, Ar), 7.33–7.48 (m, 5 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz): δ = 19.4, 33.6, 43.4, 109.2, 111.9, 115.8, 122.6, 125.5,
129.1, 129.7, 130.3, 130.4, 131.8, 137.6 ppm. IR (CH Cl ): ν =
˜
2
2
3094, 3064, 3037, 2925, 2248, 1595, 1496, 1098, 1014 cm–1. MS
(EI): m/z = 305 (28.47) [M + 2]+, 304 (24.52) [M + 1]+, 303 (81.29)
[M]+. C18H10ClN3 (303.0563): calcd. C 71.18, H 3.32, Cl 11.67, N
13.83; found C 71.43, H 3.47, N 13.98.
134.0, 138.0 ppm. IR (CH Cl ): ν = 2988, 2250, 1588, 1487,
˜
2
2
1088 cm–1. MS (EI): m/z = 385 (6.54) [M + 4]+, 384 (5.53) [M +
3]+, 383 (25.17) [M + 2]+, 382 (5.15) [M + 1]+, 381 (19.19) [M]+.
C18H9BrClN3 (380.9668): calcd. C 56.50, H 2.37, Br 20.88, Cl 9.27,
N 10.98; found C 56.46, H 2.35, N 11.00.
(2R,3R)-2-(4-Chlorophenyl)-3-phenylcyclopropane-1,1,2-tricarbo-
nitrile (3aЈ): M.p. 210–212 °C. 1H NMR (CDCl3, 300 MHz, TMS):
δ = 3.95 (s, 1 H, CH), 7.51–7.58 (m, 9 H, Ar) ppm. 13C NMR
(CDCl3, 75 MHz): δ = 20.8, 36.7, 40.7, 109.6, 110.6, 113.4, 126.7,
(2R,3R)-3-(2-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2-
tricarbonitrile (3dЈ): M.p. 208–210 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 4.03 (s, 1 H, CH), 7.11 (d, J = 8.8 Hz, 2 H, Ar), 7.30
(d, J = 8.8 Hz, 2 H, Ar), 7.37–7.48 (m, 3 H, Ar), 7.71–7.74 (m, 1
H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 19.9, 35.1, 43.6,
109.3, 111.7, 115.6, 123.4, 125.9, 126.4, 128.4, 129.2, 129.6, 130.2,
128.9, 129.7, 130.0, 130.4, 130.5, 138.0 ppm. IR (CH Cl : ν = 2999,
˜
2
2
2254, 1497, 1449, 1404, 1238, 1003 cm–1. MS (EI): m/z = 305
(24.26) [M + 2]+, 304 (20.60) [M + 1]+, 303 (70.50). HRMS (EI):
calcd. for C18H10ClN3 [M]+ 303.0563; found 303.0567.
(2R,3S)-3-(4-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2-
tricarbonitrile (3b): M.p. 196–198 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 3.86 (s, 1 H, CH), 6.89 (d, J = 8.4 Hz, 2 H, Ar), 7.21
(d, J = 8.4 Hz, 2 H, Ar), 7.43 (d, J = 8.4 Hz, 2 H, Ar), 7.50 (d, J
= 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 19.4,
33.6, 42.7, 109.0, 111.7, 115.6, 122.2, 124.5, 125.1, 130.2, 131.1,
131.8, 133.9, 137.3 ppm. IR (CH Cl ): ν = 2924, 2926, 2249, 1595,
˜
2
2
1496, 1100 cm–1. MS (EI): m/z = 385 (1.43) [M + 4]+, 384 (1.27)
[M + 3]+, 383 (5.30) [M + 2]+, 382 (1.05) [M + 1]+, 381 (3.86)
[M]+. C18H9BrClN3 (380.9668): calcd. C 56.50, H 2.37, Br 20.88,
Cl 9.27, N 10.98; found C 56.53, H 2.40, N 11.03.
131.7, 132.4, 137.9 ppm. IR (CH Cl : ν = 3039, 2925, 2248, 1594,
˜
2
2
(2R,3S)-2-(4-Chlorophenyl)-3-(2,3-dichlorophenyl)cyclopropane-
1,1,2-tricarbonitrile (3e): M.p. 246–248 °C. H NMR [(CD)3CO,
300 MHz, TMS]: δ = 4.73 (s, 1 H, CH), 7.41 (d, J = 9.0 Hz, 2 H,
Ar), 7.46–7.54 (m, 3 H, Ar), 7.71 (d, J = 7.8 Hz, 1 H, Ar), 7.77 (d,
J = 7.8 Hz, 1 H, Ar) ppm. 13C NMR [(CD)3CO, 75 MHz]: δ =
21.8, 35.6, 42.1, 110.9, 113.3, 117.0, 125.8, 129.2, 129.3, 129.5,
1492, 1402, 1012 cm–1. MS (EI): m/z = 384 (10.86) [M + 4]+, 383
(45.54) [M + 3]+, 382 (10.95) [M + 1]+, 381 (36.00) [M + 1]+, 380
(1.91) [M]+. C18H9BrClN3 (380.9668): calcd. C 56.50, H 2.37, Br
20.88, Cl 9.27, N 10.98; found C 56.56, H 2.28, N 10.91.
1
(2R,3R)-3-(4-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2-
tricarbonitrile (3bЈ): M.p. 200–202 °C. 1H NMR (CDCl3, 300 MHz,
TMS): δ = 3.89 (s, 1 H, CH), 7.43 (d, J = 8.7 Hz, 2 H, Ar), 7.51
(d, J = 8.7 Hz, 2 H, Ar), 7.55 (d, J = 8.7 Hz, 2 H, Ar), 7.67 (d, J
= 8.7 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 20.8,
36.7, 39.9, 109.4, 110.3, 113.2, 125.1, 125.7, 126.2, 129.9, 130.46,
130.1, 131.6, 132.8, 134.3, 134.5, 137.1 ppm. IR (CH Cl ): ν =
˜
2
2
2997, 2249, 1597, 1495, 1418, 1102 cm–1. MS (EI): m/z = 377 (1.71)
[M + 6]+ , 376 (2.92) [M + 5]+, 375 (13.25) [M + 4]+, 374 (9.17)
[M + 3]+, 373 (38.16) [M + 2]+, 372 (10.87) [M + 1]+, 371 (40.10)
[M]+, 336 (37.44). C18H8Cl3N3 (370.9784): calcd. C 58.02, H 2.16,
Cl 28.54, N 11.28; found C 57.92, H 2.39, N 11.28.
130.51, 133.0, 138.1 ppm. IR (CH Cl ): ν = 3002, 2924, 2844, 2249,
˜
2
2
1594, 1493, 1400, 1013 cm–1. MS (EI): m/z = 384 (8.81) [M + 4]+,
383 (39.75) [M + 3]+, 382 (8.42) [M + 1]+, 381 (29.51) [M + 1]+,
380 (2.10) [M]+. C18H9BrClN3 (380.9668): calcd. C 56.50, H 2.37,
Br 20.88, Cl 9.27, N 10.98; found C 56.38, H 2.51, N 11.09.
(2R,3R)-2-(4-Chlorophenyl)-3-(2,3-dichlorophenyl)cyclopropane-
1,1,2-tricarbonitrile (3eЈ): M.p. Ͼ250 °C (decomposed). 1H NMR
[(CD)3CO, 400 MHz, TMS]: δ = 4.84 (s, 1 H, CH), 7.61 (t, J =
8.0 Hz, 1 H, Ar), 7.69 (d, J = 8.4 Hz, 2 H, Ar), 7.83 (d, J = 8.0 Hz,
1 H, Ar), 8.00–8.03 (m, 1 H, Ar), 8.06 (d, J = 8.4 Hz, 2 H, Ar) ppm.
13C NMR [(CD)3CO, 100 MHz]: δ = 23.5, 38.0, 39.7, 111.5, 111.8,
115.1, 128.5, 129.6, 130.5, 130.7, 130.8, 132.2, 133.1, 134.4,
(2R,3S)-3-(3-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2-
1
tricarbonitrile (3c): M.p. 210–212 °C. H NMR (CDCl3, 400 MHz,
TMS): δ = 3.85 (s, 1 H, CH), 6.81–6.85 (m, 1 H, Ar), 7.18–7.23
(m, 3 H, Ar), 7.36 (t, J = 2.0 Hz, 1 H, Ar), 7.43 (d, J = 8.8 Hz, 2
H, Ar), 7.57–7.60 (m, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 19.4, 33.7, 42.3, 108.9, 111.6, 115.5, 122.2, 123.1, 127.5, 127.7,
137.8 ppm. IR (CH Cl ): ν = 2989, 2252, 1487, 1404, 1088 cm–1.
˜
2
2
MS (EI): m/z = 377 (1.84) [M + 6]+, 376 (3.19) [M + 5]+, 375
(14.69) [M + 4]+, 374 (10.70) [M + 3]+, 373 (43.39) [M + 2]+, 372
(12.57) [M + 1]+, 371 (45.07) [M]+, 336 (42.16). HRMS (EI): calcd.
for C18H8Cl3N3 [M]+ 370.9784; found 370.9782.
130.2, 130.5, 131.7, 133.3, 133.6, 137.9 ppm. IR (CH Cl ): ν =
˜
2
2
3042, 2924, 2247, 1594, 1566, 1094 cm–1. MS (EI): m/z = 385 (9.08)
[M + 4]+, 384 (9.06) [M + 3]+, 383 (33.16) [M + 2]+, 382 (10.23) [M
+ 1]+, 381 (25.88) [M]+. C18H9BrClN3 (380.9668): calcd. C 56.50, H
2.37, Br 20.88, Cl 9.27, N 10.98; found C 56.61, H 2.30, N 10.96.
(2R,3S)-2-(4-Chlorophenyl)-3-m-tolylcyclopropane-1,1,2-tricarbo-
1
nitrile (3f): M.p. 149–151 °C. H NMR (CDCl3, 300 MHz, TMS):
δ = 2.32 (s, 3 H, CH3), 3.88 (s, 1 H, CH), 6.74 (d, J = 6.6 Hz, 1 H,
(2R,3R)-3-(3-Bromophenyl)-2-(4-chlorophenyl)cyclopropane-1,1,2- Ar), 6.96 (s, 1 H, Ar), 7.18–7.24 (m, 4 H, Ar), 7.40 (d, J = 8.7 Hz,
tricarbonitrile (3cЈ): M.p. 184–186 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 3.90 (s, 1 H, CH), 7.41 (t, J = 8.0 Hz, 1 H, Ar), 7.49–
7.56 (m, 5 H, Ar), 7.66 (d, J = 8.0 Hz, 1 H, Ar), 7.69 (s, 1 H,
Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 20.8, 36.6, 39.6, 109.3,
110.3, 113.1, 123.5, 126.2, 127.4, 128.8, 130.0, 130.5, 131.2, 132.2,
2 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 19.4, 21.3, 33.6,
43.4, 109.2, 112.0, 115.9, 122.7, 125.3, 126.2, 128.9, 129.9, 130.7,
131.1, 131.8, 137.5, 139.2 ppm. IR (CH Cl ): ν = 3096, 3036, 2924,
˜
2
2
2867, 2248, 1597, 1494, 1098 cm–1. MS (EI): m/z = 319 (33.79) [M
+ 2]+, 318 (33.14) [M + 1]+, 317 (100.00) [M]+, 302 (28.26). HRMS
(EI): calcd. for C19H12ClN3 [M]+ 317.0720; found 317.0726.
133.8, 138.1 ppm. IR (CH Cl ): ν = 3011, 2925, 2854, 2249, 1596,
˜
2
2
Eur. J. Org. Chem. 2010, 1977–1988
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1983

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
(2R,3R)-2-(4-Chlorophenyl)-3-m-tolylcyclopropane-1,1,2-tricarbo-
34.2, 40.9, 108.9, 111.7, 115.7, 122.7, 123.0, 123.5, 130.0, 130.4,
nitrile (3fЈ): M.p. 179–181 °C. 1H NMR (CDCl3, 300 MHz, TMS): 131.5, 135.8, 151.2, 151.4 ppm. IR (CH Cl ): ν = 3036, 2959, 2926,
˜
2
2
δ = 2.42 (s, 3 H, CH3), 3.91 (s, 1 H, CH), 7.30–7.44 (m, 4 H, Ar),
7.49–7.55 (m, 4 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 20.8,
21.3, 36.7, 40.6, 109.6, 110.7, 113.4, 125.8, 126.6, 126.7, 129.4,
2249, 1591, 1574, 1494, 1025 cm–1. MS (EI): m/z = 270 (100.00)
[M]+, 269 (73.89), 243 (28.41). C17H10N4 (270.0905): calcd. C 75.54,
H 3.73, N 20.73; found C 75.82, H 3.49, N 20.71.
129.5, 130.0, 130.4, 131.3, 137.9, 139.7 ppm. IR (CH Cl ): ν =
˜
2
2
(2R,3R)-2-Phenyl-3-(pyridin-3-yl)cyclopropane-1,1,2-tricarbonitrile
(3iЈ): M.p. 225–226 °C. 1H NMR (CDCl3, 300 MHz, TMS): δ =
3.97 (s, 1 H, CH), 7.51 (dd, J1 = 5.1, J2 = 7.8 Hz, 1 H, Ar), 7.60–
7.61 (m, 5 H, Ar), 7.99 (d, J = 7.8 Hz, 1 H, Ar), 8.80 (d, J = 3.6 Hz,
1 H, Ar), 8.87 (s, 1 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ =
20.6, 37.1, 37.9, 109.4, 110.2, 113.3, 124.1, 127.5, 128.6, 130.3,
3096, 3018, 2924, 2860, 2248, 1671, 1607, 1596, 1496, 1405 cm–1.
MS (EI): m/z = 319 (35.02) [M + 2]+, 318 (33.63) [M + 1]+, 317
(100.00) [M]+, 302 (26.27). C19H12ClN3 (317.0720): calcd. C 71.81,
H 3.81, Cl 11.16, N 13.22; found C 71.64, H 3.70, N 13.22.
(2R,3S)-2-(4-Chlorophenyl)-3-(4-methoxyphenyl)cyclopropane-1,1,2-
1
tricarbonitrile (3g): Liquid. H NMR (CDCl3, 400 MHz, TMS): δ
131.8, 136.0, 150.5, 151.6 ppm. IR (CH Cl ): ν = 2970, 2919, 2249,
˜
2
2
1573, 1483, 1451, 1417 cm–1. MS (EI): m/z = 270 (100.00) [M]+,
269 (71.66), 243 (28.07). C17H10N4 (270.0905): calcd. C 75.54, H
3.73, N 20.73; found C 75.67, H 3.46, N 20.95.
= 3.81 (s, 3 H, OCH3), 3.85 (s, 1 H, CH), 6.86 (d, J = 8.8 Hz, 2 H,
Ar), 6.94 (d, J = 8.8 Hz, 2 H, Ar), 7.22 (d, J = 8.8 Hz, 2 H, Ar),
7.42 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 19.3, 33.3, 43.5, 55.4, 109.4, 112.0, 114.6, 115.9, 117.0, 122.8,
(2R,3S)-2-(4-Chlorophenyl)-3-[(E)-styryl]cyclopropane-1,1,2-tri-
carbonitrile (3j): M.p. 122–124 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 3.60 (d, J = 10.0 Hz, 1 H, CH), 5.42 (dd, J1 = 10.0, J2
= 16.0 Hz, 1 H, CH), 7.11 (d, J = 16.0 Hz, 1 H, CH), 7.32–7.38
(m, 5 H, Ar), 7.43 (d, J = 8.4 Hz, 2 H, Ar), 7.52 (d, J = 8.4 Hz, 2
H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 18.6, 32.6, 42.8,
109.2, 111.3, 114.3, 115.2, 123.6, 127.0, 129.0, 129.9, 130.5, 131.8,
130.0, 131.1, 131.9, 137.6, 161.0 ppm. IR (CH Cl ): ν = 2960, 2935,
˜
2
2
2841, 2247, 1610, 1517, 1494, 1259, 1185 cm–1. MS (EI): m/z = 335
(35.43) [M + 2]+, 334 (28.04) [M + 1]+, 333 (100.00) [M]+, 298
(41.03). HRMS (EI): calcd. for C19H12ClN3O [M]+ 333.0669; found
333.0666.
(2R,3R)-2-(4-Chlorophenyl)-3-(4-methoxyphenyl)cyclopropane-
1,1,2-tricarbonitrile (3gЈ): M.p. 210–212 °C. 1H NMR (CDCl3,
400 MHz, TMS): δ = 3.84 (s, 3 H, OCH3), 3.89 (s, 1 H, CH), 7.02
(d, J = 8.8 Hz, 2 H, Ar), 7.48 (d, J = 8.8 Hz, 2 H, Ar), 7.50–7.55
(m, 4 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 21.0, 36.8,
40.4, 55.4, 109.7, 110.7, 113.6, 115.1, 118.3, 126.8, 130.0, 130.3,
134.3, 137.9, 141.8 ppm. IR (CH Cl ): ν = 3030, 2248, 1597, 1494,
˜
2
2
1096 cm–1. MS (EI): m/z = 331 (11.65) [M + 2]+, 330 (21.23) [M +
1]+, 329 (35.94) [M]+, 328 (45.30), 294 (55.38). HRMS (EI): calcd.
for C20H12ClN3 [M]+ 329.0720; found 329.0724.
(2R,3R)-2-(4-Chlorophenyl)-3-[(E)-styryl]cyclopropane-1,1,2-tri-
carbonitrile (3jЈ): M.p. 212–214 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 3.52 (d, J = 8.8 Hz, 1 H, CH), 6.12 (dd, J1 = 8.8, J2 =
15.6 Hz, 1 H, CH), 7.16 (d, J = 15.6 Hz, 1 H, CH), 7.39–7.44 (m,
3 H, Ar), 7.45–7.54 (m, 6 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz): δ = 20.5, 35.9, 40.1, 109.8, 110.2, 113.4, 114.8, 125.9,
127.1, 129.0, 129.9, 130.4, 131.7, 134.2, 137.9, 142.4 ppm. IR
130.4, 137.8, 161.0 ppm. IR (CH Cl ): ν = 3007, 2965, 2937, 2841,
˜
2
2
2248, 1612, 1517, 1256, 1097 cm–1. MS (EI): m/z = 335 (36.52) [M
+ 2]+, 334 (26.88) [M + 1]+, 333 (100.00) [M]+, 298 (61.44).
C19H12ClN3O (333.0669): calcd. C 68.37, H 3.62, Cl 10.62, N
12.59, O 4.79; found C 68.29, H 3.74, N 12.66.
(2R,3S)-2-(4-Chlorophenyl)-3-(naphthalen-1-yl)cyclopropane-1,1,2-
tricarbonitrile (3h): M.p. 208–210 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 4.31 (s, 1 H, CH), 6.96 (d, J = 8.8 Hz, 2 H, Ar), 7.09
(d, J = 8.8 Hz, 2 H, Ar), 7.51 (dd, J1 = 7.2, J2 = 8.0 Hz, 1 H, Ar),
7.57–7.62 (m, 2 H, Ar), 7.69 (dt, J1 = 0.8, J2 = 7.2 Hz, 1 H, Ar),
7.82–7.85 (m, 1 H, Ar), 7.93–7.99 (m, 2 H, Ar) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 19.5, 35.1, 41.8, 109.6, 112.1, 116.1, 121.9,
122.3, 123.4, 125.4, 126.5, 127.2, 128.3, 129.3, 129.4, 130.3, 131.1,
(CH Cl ): ν = 3031, 2925, 2854, 2248, 1596, 1496, 1097 cm–1. MS
˜
2
2
(EI): m/z = 331 (13.90) [M + 2]+, 330 (22.98) [M + 1]+, 329 (41.14)
[M]+, 328 (45.30), 302 (64.37). HRMS (EI): calcd. for C20H12ClN3
[M]+ 329.0720; found 329.0725.
2-(4-Chlorophenyl)-3-ethylcyclopropane-1,1,2-tricarbonitrile (3k +
1
3kЈ): H NMR (CDCl3, 300 MHz, TMS): δ = 1.20–1.35 (m, 3 H,
CH3), 1.95–2.16 (m, 2 H, CH2), 2.65–2.73 (m, 1 H, CH), 7.37–7.42
(m, 2 H, Ar), 7.47–7.51 (m, 2 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz): δ = 11.6, 11.7, 17.1, 19.6, 20.5, 21.2, 33.5, 36.3, 38.6,
41.8, 109.3, 109.8, 110.6, 111.9, 113.5, 115.6, 123.7, 126.3, 129.9,
131.4, 133.5, 137.1 ppm. IR (CH Cl ): ν = 3063, 3002, 2246, 1595,
˜
2
2
1510, 1495, 1099 cm–1. MS (EI): m/z = 355 (5.78) [M + 2]+, 354
(5.65) [M + 1]+, 353 (15.48) [M]+, 326 (18.52). C22H12ClN3
(353.0720): calcd. C 74.68, H 3.42, Cl 10.02, N 11.88; found C
74.85, H 3.73, N 11.99.
130.2, 130.4, 131.3, 137.5, 137.7 ppm. IR (CH Cl ): ν = 3036, 2976,
˜
2
2
2940, 2882, 2248, 1595, 1494, 1462, 1404, 1097, 1015 cm–1. MS
(EI): m/z = 257 (5.06) [M + 2]+, 352 (3.40) [M + 1]+, 351 (15.31)
[M]+. HRMS (EI): calcd. for C14H10ClN3 [M]+ 255.0563; found
255.0559.
(2R,3R)-2-(4-Chlorophenyl)-3-(naphthalen-1-yl)cyclopropane-1,1,2-
tricarbonitrile (3hЈ): M.p. 257–259 °C. 1H NMR [(CD)3CO,
400 MHz, TMS]: δ = 5.18 (s, 1 H, CH), 7.65–7.70 (m, 2 H, Ar),
7.71–7.77 (m, 3 H, Ar), 8.06 (d, J = 8.4 Hz, 1 H, Ar), 8.08–8.15
(m, 5 H, Ar) ppm. 13C NMR [(CD)3CO, 100 MHz]: δ = 23.3, 37.6,
39.4, 111.7, 112.2, 115.5, 123.7, 125.5, 126.1, 127.6, 128.5, 128.8,
129.1, 130.2, 130.8, 131.6, 132.1, 132.4, 134.9, 137.7 ppm. IR
(2R,3S)-2-(3,5-Dimethylphenyl)-3-phenylcyclopropane-1,1,2-tri-
carbonitrile (3l): M.p. 193–195 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 2.26 (s, 6 H, CH3), 3.84 (s, 3 H, CH), 6.85 (s, 2 H, Ar),
7.03 (d, J = 8.0 Hz, 2 H, Ar), 7.09 (s, 1 H, Ar), 7.32 (t, J = 8.4 Hz,
2 H, Ar), 7.41 (t, J = 8.0 Hz, 1 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz): δ = 19.2, 21.1, 34.3, 43.4, 109.4, 112.3, 116.4, 123.7,
(CH Cl ): ν = 3068, 2980, 2250, 1594, 1504, 1487, 1402 cm–1. MS
˜
2
2
(EI): m/z = 355 (25.58) [M + 2]+, 354 (27.83) [M + 1]+, 353 (72.83)
[M]+, 326 (70.12). C22H12ClN3 (353.0720): calcd. C 74.68, H 3.42,
Cl 10.02, N 11.88; found C 74.64, H 3.75, N 11.94.
126.1, 128.0, 128.7, 129.8, 130.0, 132.6, 139.5 ppm. IR (CH Cl ): ν
˜
2
2
= 3035, 2957, 2922, 2247, 1607, 1499, 1457, 853 cm–1. MS (EI): m/z
= 297 (100.00), 282 (55.36), 270 (48.23), 255 (49.06). HRMS (EI):
calcd. for C20H15N3 [M]+ 297.1266; found 297.1258.
(2R,3S)-2-Phenyl-3-(pyridin-3-yl)cyclopropane-1,1,2-tricarbonitrile
(3i): M.p. 187–188 °C. 1H NMR (CDCl3, 400 MHz, TMS): δ =
3.95 (s, 1 H, CH), 6.93–6.96 (m, 1 H, Ar), 7.16 (dd, J1 = 4.8, J2 =
8.4 Hz, 1 H, Ar), 7.29–7.32 (m, 2 H, Ar), 7.45–7.50 (m, 2 H, Ar), (2R,3R)-2-(3,5-Dimethylphenyl)-3-phenylcyclopropane-1,1,2-tri-
7.52–7.57 (m, 1 H, Ar), 8.58 (d, J = 2.0 Hz, 1 H, Ar), 8.66 (d, J =
carbonitrile (3lЈ): M.p. 235–236 °C. 1H NMR (CDCl3, 300 MHz,
3.6 Hz, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 19.2, TMS): δ = 2.39 (s, 6 H, CH3), 3.97 (s, 1 H, CH), 7.17 (s, 3 H, Ar),
1984
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 1977–1988

Probing Phosphane-Mediated [2+1] Annulation Reactions
7.50–7.60 (m, 5 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 20.6,
21.2, 37.4, 40.4, 109.9, 110.9, 114.0, 126.3, 127.2, 127.9, 129.0,
7.52 (m, 1 H, Ar), 7.56 (d, J = 8.0 Hz, 1 H, Ar) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 20.1, 33.0, 43.8, 109.3, 111.9, 114.9, 122.7,
126.2, 127.5, 128.9, 129.4, 130.3, 131.3, 132.2, 132.8, 136.6 ppm.
129.6, 130.3, 133.2, 140.0 ppm. IR (CH Cl ): ν = 3002, 2958, 2924,
˜
2
2
2250, 2230, 1593, 1570, 1447, 1318 cm–1. MS (EI): m/z = 297
(100.00), 282 (30.56), 270 (63.89), 255 (45.34). HRMS (EI): calcd.
for C20H15N3 [M]+ 297.1266; found 297.1270.
IR (CH Cl ): ν = 3065, 3037, 2925, 2854, 2248, 1590, 1500, 1475,
˜
2 2
1442, 1040 cm–1. MS (EI): m/z = 305 (12.97) [M + 2]+, 304 (10.86)
[M + 1]+, 303 (38.53) [M]+, 268 (97.37). HRMS (EI): calcd. for
C18H10ClN3 [M]+ 303.0563; found 303.0561.
(2R,3S)-3-Phenyl-2-(p-tolyl)cyclopropane-1,1,2-tricarbonitrile (3m):
1
M.p. 180–182 °C. H NMR (CDCl3, 300 MHz, TMS): δ = 2.38 (s,
(2R,3S)-2,3-Diphenylcyclopropane-1,1,2-tricarbonitrile (3p): M.p.
1
3 H, CH3), 3.86 (s, 1 H, CH), 7.04 (d, J = 7.8 Hz, 2 H, Ar), 7.14 180–181 °C. H NMR (CDCl3, 300 MHz, TMS): δ = 3.90 (s, 1 H,
(d, J = 8.4 Hz, 2 H, Ar), 7.22 (d, J = 8.4 Hz, 2 H, Ar), 7.33 (t, J
CH), 7.02 (d, J = 7.5 Hz, 2 H, Ar), 7.25–7.35 (m, 4 H, Ar), 7.39–
= 7.8 Hz, 2 H, Ar), 7.39–7.45 (m, 1 H, Ar) ppm. 13C NMR (CDCl3, 7.52 (m, 4 H, Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 19.3,
75 MHz): δ = 19.3, 21.3, 34.3, 43.5, 109.4, 112.3, 116.3, 121.0, 34.3, 43.4, 109.3, 112.2, 116.2, 124.1, 125.9, 128.9, 129.6, 129.7,
126.0, 128.9, 129.8, 130.1, 130.3, 141.5 ppm. IR (CH Cl ): ν =
130.1, 130.4, 131.0 ppm. IR (CH Cl ): ν = 3063, 3040, 2925, 2248,
˜
2 2
˜
2
2
3036, 2924, 2248, 1513, 1500, 1457, 1267 cm–1. MS (EI): m/z =
283 (100.00) [M]+, 268 (50.24), 256 (57.23). HRMS (EI): calcd. for
C19H13N3 [M]+ 283.1109; found 283.1110.
1495, 1451 cm–1. MS (EI): m/z = 269 (93.39) [M]+, 268 (100.00),
242 (94.37). C18H11N3 (269.0953): calcd. C 80.28, H 4.12, N 15.60;
found C 80.15, H 4.08, N 15.71.
(2R,3R)-3-Phenyl-2-(p-tolyl)cyclopropane-1,1,2-tricarbonitrile (2R,3R)-2,3-Diphenylcyclopropane-1,1,2-tricarbonitrile (3pЈ): M.p.
1
1
(3mЈ): M.p. 220–222 °C. H NMR (CDCl3, 400 MHz, TMS): δ = 260–262 °C. H NMR [(CD)2CO, 400 MHz, TMS]: δ = 4.75 (s, 1
2.43 (s, 3 H, CH3), 3.96 (s, 1 H, CH), 7.35 (d, J = 8.8 Hz, 2 H,
Ar), 7.46 (d, J = 8.8 Hz, 2 H, Ar), 7.50–7.59 (m, 5 H, Ar) ppm.
H, CH), 7.53–7.64 (m, 6 H, Ar), 7.82 (d, J = 7.2 Hz, 2 H, Ar),
7.95–7.97 (m, 2 H, Ar) ppm. 13C NMR [(CD)2CO, 100 MHz]: δ =
13C NMR (CDCl3, 100 MHz): δ = 20.8, 21.3, 37.3, 40.5, 109.9, 22.2, 38.1, 40.9, 111.8, 112.2, 115.5, 129.8, 130.0, 130.3, 130.41,
110.9, 113.9, 125.2, 127.2, 128.5, 129.0, 129.6, 130.4, 130.7, 130.44, 130.6, 131.9 ppm. IR (CH Cl ): ν = 2998, 2918, 2253, 1493,
˜
2
2
142.0 ppm. IR (CH Cl ): ν = 3004, 2998, 2252, 1516, 1514, 1449,
1450 cm–1. MS (EI): m/z = 269 (93.12) [M]+, 268 (97.41), 242
(100.00). HRMS (EI): calcd. for C18H11N3 [M]+ 269.0953; found
269.0952.
˜
2
2
1239 cm–1. MS (EI): m/z = 283 (100.00) [M]+, 268 (39.21), 256
(46.21). C19H13N3 (283.1109): calcd. C 80.54, H 4.62, N 14.83;
found C 80.98, H 4.13, N 15.05.
(2R,3S)-3-(3-Bromophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
1
(2R,3S)-2-(4-Bromophenyl)-3-phenylcyclopropane-1,1,2-tricarbo- nitrile (3q): M.p. 107–109 °C. H NMR (CDCl3, 400 MHz, TMS):
1
nitrile (3n): M.p. 223–225 °C. H NMR (CDCl3, 300 MHz, TMS): δ = 3.84 (s, 1 H, CH), 6.82 (d, J = 8.0 Hz, 2 H, Ar), 7.17 (t, J =
δ = 3.92 (s, 1 H, CH), 7.05 (d, J = 7.8 Hz, 2 H, Ar), 7.13 (d, J =
8.1 Hz, 2 H, Ar), 7.35 (t, J = 8.1 Hz, 2 H, Ar), 7.42–7.47 (m, 1 H,
Ar), 7.55 (d, J = 8.1 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz): δ = 19.4, 33.7, 43.3, 109.2, 111.9, 115.8, 123.1, 125.5,
8.0 Hz, 1 H, Ar), 7.26–7.30 (m, 3 H, Ar), 7.43–7.48 (m, 2 H, Ar),
7.50–7.57 (m, 2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ =
19.4, 34.4, 42.4, 109.0, 111.8, 115.9, 122.9, 123.7, 127.8, 128.0,
129.8, 130.2, 130.4, 131.3, 133.2, 133.3 ppm. IR (CH Cl ): ν =
˜
2
2
125.9, 129.1, 129.7, 130.3, 131.9, 132.9 ppm. IR (CH Cl ): ν =
3063, 3037, 2925, 2248, 1595, 1567, 1479, 1079 cm–1. MS (EI): m/z
˜
2
2
3092, 3036, 2925, 2245, 2254, 1587, 1498, 1484, 1011 cm–1. MS = 349 (27.12) [M + 2]+, 348 (11.41) [M + 1]+, 347 (27.24) [M]+,
(EI): m/z = 349 (38.16) [M + 2]+, 348 (14.95) [M + 1]+, 347 (36.67)
268 (97.88), 241 (100.00). HRMS (EI): calcd. for C18H10BrN3
[M]+, 268 (99.64), 241 (95.96). C18H10BrN3 (347.0058): calcd. C [M]+ 347.0058; found 347.0055.
62.09, H 2.89, Br 22.95, N 12.07; found C 62.39, H 3.14, N 12.16.
(2R,3R)-3-(3-Bromophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
(2R,3R)-2-(4-Bromophenyl)-3-phenylcyclopropane-1,1,2-tricarbo- nitrile (3qЈ): M.p. 184–185 °C. 1H NMR (CDCl3, 400 MHz, TMS):
nitrile (3nЈ): M.p. 245–247 °C. 1H NMR (CDCl3, 400 MHz, TMS):
δ = 3.94 (s, 1 H, CH), 7.47 (d, J = 8.4 Hz, 2 H, Ar), 7.53–7.58 (m,
δ = 3.94 (s, 1 H, CH), 7.41 (t, J = 7.6 Hz, 1 H, Ar), 7.52–7.55 (m,
1 H, Ar), 7.56–7.58 (m, 5 H, Ar), 7.64–7.66 (m, 1 H, Ar), 7.71–
5 H, Ar), 7.72 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 7.72 (m, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 20.7,
100 MHz): δ = 20.8, 36.8, 40.7, 109.5, 110.7, 113.3, 126.3, 126.7,
127.3, 129.0, 129.8, 130.2, 130.6, 133.4 ppm. IR (CH Cl ): ν =
37.3, 39.5, 109.6, 110.4, 113.5, 123.5, 127.4, 127.7, 128.6, 129.1,
130.2, 131.2, 131.6, 132.2, 133.7 ppm. IR (CH Cl ): ν = 3064, 3012,
˜
˜
2
2
2
2
2996, 2253, 1490, 1449, 1398, 1239 cm–1. MS (EI): m/z = 349
2248, 1598, 1567, 1495, 1478, 1451, 1421, 1074 cm–1. MS (EI): m/z
(38.73) [M + 2]+, 348 (15.02) [M + 1]+, 347 (38.30) [M]+, 268 = 349 (19.82) [M + 2]+, 348 (9.19) [M + 1]+, 347 (19.94) [M]+, 268
(98.21), 241 (100.00). C18H10BrN3 (347.0058): calcd. C 62.09, H
2.89, Br 22.95, N 12.07; found C 62.35, H 3.12, N 12.06.
(94.12), 241 (100.00). C18H10BrN3 (347.0058): calcd. C 62.09, H
2.89, Br 22.95, N 12.07; found C 62.10, H 2.89, N 12.07.
(2R,3S)-2-(2-Chlorophenyl)-3-phenylcyclopropane-1,1,2-tricarbo-
(2R,3S)-3-(4-Bromophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
1
1
nitrile (3o): M.p. 174–176 °C. H NMR (CDCl3, 400 MHz, TMS): nitrile (3r): M.p. 206–208 °C. H NMR (CDCl3, 300 MHz, TMS):
δ = 3.87 (s, 1 H, CH), 7.44–7.52 (m, 2 H, Ar), 7.53–7.58 (m, 4 H, δ = 3.83 (s, 1 H, CH), 6.86 (d, J = 8.7 Hz, 2 H, Ar), 7.26–7.29 (m,
Ar), 7.62–7.67 (m, 3 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ
3 H, Ar), 7.42–7.56 (m, 5 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz): δ = 19.3, 34.2, 42.8, 109.1, 111.9, 116.0, 123.8, 124.9,
= 20.6, 36.0, 42.6, 109.6, 110.8, 112.3, 126.9, 127.2, 128.3, 129.0,
129.7, 130.5, 131.0, 131.3, 133.0, 136.1 ppm. IR (CH Cl ): ν =
129.8, 130.4, 131.2, 132.2 ppm. IR (CH Cl ): ν = 3032, 2960, 2925,
˜
2 2
˜
2
2
3064, 3000, 2925, 2249, 1499, 1475, 1446, 1058 cm–1. MS (EI): m/z
= 305 (17.44) [M + 2]+, 304 (13.41) [M + 1]+, 303 (49.24) [M]+,
268 (100.00). C18H10ClN3 (303.0563): calcd. C 71.18, H 3.32, Cl
11.67, N 13.83; found C 71.19, H 3.32, N 13.83.
2854, 2247, 1582, 1592, 1491, 1450, 1076 cm–1. MS (EI): m/z = 349
(34.03) [M + 2]+, 348 (12.47) [M + 1]+, 347 (31.91) [M]+, 268
(100.00), 241 (92.60). HRMS (EI): calcd. for C18H10BrN3 [M]+
347.0058; found 347.0064.
(2R,3R)-(2-Chlorophenyl)-3-phenylcyclopropane-1,1,2-tricarbonitrile
(3oЈ): M.p. 196–198 °C. 1H NMR (CDCl3, 400 MHz, TMS): δ =
3.92 (s, 1 H, CH), 7.05 (d, J = 7.6 Hz, 2 H, Ar), 7.20–7.23 (m, 1
(2R,3R)-3-(4-Bromophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
nitrile (3rЈ): M.p. 233–235 °C. 1H NMR (CDCl3, 400 MHz, TMS):
δ = 3.92 (s, 1 H, CH), 7.46 (d, J = 8.4 Hz, 2 H, Ar), 7.57–7.60 (m,
H, Ar), 7.25–7.35 (m, 3 H, Ar), 7.44 (t, J = 7.2 Hz, 1 H, Ar), 7.47– 5 H, Ar), 7.69 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
Eur. J. Org. Chem. 2010, 1977–1988
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1985

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
100 MHz): δ = 20.7, 37.4, 39.8, 109.6, 110.5, 113.6, 125.1, 126.0,
100 MHz): δ = 14.0, 32.5, 33.3, 40.9, 64.9, 112.5, 116.3, 125.2,
127.9, 128.6, 130.2, 130.6, 131.7, 133.0 ppm. IR (CH Cl ): ν =
127.6, 128.7, 129.3, 129.6, 129.7, 132.1, 136.6, 162.9 ppm. IR
˜
2
2
3003, 2251, 1492, 1397, 1012 cm–1. MS (EI): m/z = 349 (38.00) [M
(CH Cl ): ν = 3096, 2986, 2240, 1746, 1495, 1241 cm–1. MS (ESI):
˜
2
2
+ 2]+, 348 (14.27) [M + 1]+, 347 (37.74) [M]+, 268 (100.00), 241
m/z = 351.0 [M + 1]+. HRMS (ESI) calcd. for C20H15ClN2O2 [M+
(99.87). C18H10ClN3 (303.0563): calcd. C 62.09, H 2.89, Br 22.95, + Na] 373.0720; found 373.07094.
N 12.07; found C 62.25, H 3.05, N 12.08.
Ethyl
2-(4-Chlorophenyl)-1,2-dicyano-3-phenylcyclopropanecarb-
oxylate (5aЈ): M.p. 166–168 °C. 1H NMR (CDCl3, 300 MHz,
TMS): δ = 1.18 (t, J = 6.6 Hz, 3 H, CH3), 4.12 (s, 1 H, CH), 4.13
(q, J = 6.6 Hz, 2 H, CH2), 7.42–7.43 (m, 4 H, Ar), 7.46–7.52 (m,
3 H, Ar), 7.55–7.58 (m, 2 H, Ar) ppm. 13C NMR (CDCl3,
75 MHz): δ = 13.8, 34.2, 36.7, 37.9, 64.3, 112.9, 115.0, 127.9, 128.7,
(2R,3S)-3-(4-Chlorophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
nitrile (3s): M.p. 228–230 °C. 1H NMR [(CD3)2CO, 400 MHz,
TMS]: δ = 4.60 (s, 1 H, CH), 7.19 (d, J = 8.4 Hz, 2 H, Ar), 7.41
(d, J = 8.4 Hz, 2 H, Ar), 7.49–7.54 (m, 2 H, Ar), 7.55–7.60 (m, 1
H, Ar), 7.62–7.65 (m, 2 H, Ar) ppm. 13C NMR [(CD3)2CO,
100 MHz]: δ = 20.8, 35.0, 42.8, 111.1, 113.7, 117.5, 126.3, 127.5,
129.0, 129.3, 129.5, 129.6, 130.4, 136.6, 161.3 ppm. IR (CH Cl ): ν
˜
2
2
= 3091, 3032, 2985, 2245, 1744, 1496, 1293, 1096 cm–1. MS (ESI):
m/z = 351.0 [M + 1]+. HRMS (ESI) calcd. for C20H15ClN2O2 [M+
+ Na] 373.0720; found 373.07077.
129.3, 130.4, 131.8, 131.9, 132.8, 136.1 ppm. IR (CH Cl ): ν =
˜
2
2
3037, 2247, 1593, 1496 1094, 1020 cm–1. MS (EI): m/z = 305 (28.80)
[M + 2]+, 304 (24.53) [M + 1]+, 303 (82.88), 268 (100.00), 241
(97.59). HRMS (EI): calcd. for C18H10ClN3 [M]+ 303.0563; found
303.0562.
Ethyl 3-(2-Chlorophenyl)-2-(4-chlorophenyl)-1,2-dicyanocycloprop-
anecarboxylate (5b): Liquid. 1H NMR (CDCl3, 400 MHz, TMS):
δ = 1.47 (t, J = 7.2 Hz, 3 H, CH3), 4.24 (s, 1 H, CH), 4.52 (qd, J1
= 2.0, J2 = 7.2 Hz, 2 H, CH2), 7.15 (d, J = 8.8 Hz, 2 H, Ar), 7.25–
7.30 (m, 3 H, Ar), 7.39 (t, J = 7.6 Hz, 1 H, Ar), 7.44 (d, J = 8.0 Hz,
1 H, Ar), 7.52 (dd, J1 = 0.8, J2 = 8.0 Hz, 1 H, Ar) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 14.1, 33.3, 33.4, 38.6, 65.1, 112.7, 116.0,
125.8, 126.6, 127.5, 129.0, 129.3, 130.2, 130.6, 130.7, 136.0, 136.4,
(2R,3R)-3-(4-Chlorophenyl)-2-phenylcyclopropane-1,1,2-tricarbo-
nitrile (3sЈ): M.p. 210–211 °C. 1H NMR (CDCl3, 300 MHz, TMS):
δ = 3.95 (s, 1 H, CH), 7.50–7.55 (m, 4 H, Ar), 7.55–7.60 (m, 5 H,
Ar) ppm. 13C NMR (CDCl3, 75 MHz): δ = 20.8, 37.4, 39.7, 109.7,
110.5, 113.6, 125.5, 127.8, 128.6, 130.0, 130.2, 130.4, 131.6,
136.8 ppm. IR (CH Cl ): ν = 3003, 2250, 1495, 1450, 1238,
˜
2
2
1092 cm–1. MS (EI): m/z = 305 (24.10) [M + 2]+, 304 (20.85) [M +
1]+, 303 (74.76), 268 (100.00), 241 (97.91). HRMS (EI): calcd. for
C18H10ClN3 [M]+ 303.0563; found 303.0566.
162.6 ppm. IR (CH Cl ): ν = 2987, 2938, 2245, 1747, 1595, 1495,
˜
2
2
1443, 1240 cm–1. MS (EI): m/z = 388 (2.52) [M + 4]+, 387 (5.80)
[M + 3]+, 386 (8.08) [M + 2]+, 385 (9.56) [M + 1]+, 384 (9.78)
[M]+. HRMS (EI): calcd. for C20H14Cl2N2O2 [M]+ 384.0432; found
384.0439.
(2R,3S)-2-(Naphthalen-1-yl)-3-phenylcyclopropane-1,1,2-tricarbo-
1
nitrile (3t): M.p. 245–246 °C. H NMR (CDCl3, 400 MHz, TMS):
δ = 4.05 (s, 1 H, CH), 6.92–6.94 (m, 2 H, Ar), 7.16 (t, J = 7.2 Hz,
2 H, Ar), 7.29 (t, J = 7.2 Hz, 1 H, Ar), 7.44–7.61 (m, 4 H, Ar),
7.80 (s, 1 H, Ar), 7.90–7.93 (m, 1 H, Ar), 8.02 (d, J = 8.4 Hz, 1 H,
Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 19.6, 33.0, 44.0, 109.5,
112.4, 116.1, 119.9, 122.8, 125.0, 126.4, 127.0, 128.1, 128.7, 129.3,
Ethyl 3-(2-Chlorophenyl)-2-(4-chlorophenyl)-1,2-dicyanocycloprop-
anecarboxylate (5bЈ): Liquid. H NMR (CDCl3, 400 MHz, TMS):
1
δ = 1.17 (t, J = 7.2 Hz, 3 H, CH3), 4.10 (s, 1 H, CH), 4.14 (q, J =
7.2 Hz, 2 H, CH2), 7.40–7.46 (m, 4 H, Ar), 7.51 (d, J = 8.8 Hz, 2
H, Ar), 7.55–7.58 (m, 1 H, Ar), 7.68–7.71 (m, 1 H, Ar) ppm. 13C
NMR (CDCl3, 100 MHz): δ = 13.9, 34.7, 36.2, 37.0, 64.3, 112.9,
115.0, 127.3, 127.4, 127.6, 129.6, 130.3, 130.4, 130.5, 131.0, 135.4,
129.4, 130.1, 130.4, 130.8, 132.3, 134.0 ppm. IR (CH Cl ): ν =
˜
2
2
3064, 3037, 2925, 2246, 1510, 1499, 1458 cm–1. MS (EI): m/z =
319 (88.43) [M]+, 292 (100.00), 241 (69.99). HRMS (EI): calcd. for
C22H13N3 [M]+ 319.1109; found 319.1106.
136.7, 161.1 ppm. IR (CH Cl ): ν = 3067, 2986, 2938, 2247, 1746,
˜
2
2
1596, 1495, 1296 cm–1. MS (EI): m/z = 388 (0.89) [M + 4]+, 387
(1.04) [M + 3]+, 386 (4.18) [M + 2]+, 385 (2.04) [M + 1]+, 384 (6.23)
[M]+. HRMS (EI): calcd. for C20H14Cl2N2O2 [M]+ 384.0432; found
384.0434.
(2R,3R)-2-(Naphthalen-1-yl)-3-phenylcyclopropane-1,1,2-tricarbo-
nitrile (3tЈ): M.p. 272–274 °C. 1H NMR [(CD3)2CO, 400 MHz,
TMS]: δ = 4.88 (s, 1 H, CH), 7.56–7.66 (m, 3 H, Ar), 7.68–7.72 (m,
1 H, Ar), 7.77 (t, J = 8.0 Hz, 1 H, Ar), 7.92–7.96 (m, 3 H, Ar),
8.13 (d, J = 7.2 Hz, 1 H, Ar), 8.18 (d, J = 8.8 Hz, 1 H, Ar), 8.25
(d, J = 8.4 Hz, 1 H, Ar) ppm. 13C NMR [(CD3)2CO, 100 MHz]: δ
= 21.6, 36.9, 42.3, 111.9, 112.1, 115.2, 123.1, 126.1, 126.5, 129.5,
129.7, 130.2, 130.5, 130.7, 130.8, 130.9, 131.7, 133.3, 135.1 ppm.
Ethyl 3-(4-Bromophenyl)-2-(4-chlorophenyl)-1,2-dicyanocycloprop-
anecarboxylate (5c): M.p. 161–163 °C. 1H NMR (CDCl3,
400 MHz, TMS): δ = 1.46 (t, J = 7.6 Hz, 3 H, CH3), 3.95 (s, 1 H,
CH), 4.47–4.53 (m, 2 H, CH2), 6.96 (d, J = 8.8 Hz, 2 H, Ar), 7.20
(d, J = 8.8 Hz, 2 H, Ar), 7.38 (d, J = 8.8 Hz, 2 H, Ar), 7.44 (d, J
= 8.8 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 14.0,
32.5, 33.2, 40.2, 65.1, 112.3, 116.0, 123.9, 124.8, 126.7, 129.8, 131.3,
IR (CH Cl ): ν = 3000, 2244, 1509, 1448, 1217 cm–1. MS (EI): m/z
˜
2
2
= 319 (82.31) [M]+, 292 (100.00), 241 (88.41). HRMS (EI): calcd.
for C22H13N3 [M]+ 319.1109; found 319.1114.
131.9, 132.1, 136.9, 162.7 ppm. IR (CH Cl ): ν = 2984, 2926, 2854,
˜
2
2
2240, 1746, 1594, 1492, 1242, 1011 cm–1. MS (EI): m/z = 432 (0.66)
[M + 4]+, 431 (0.61) [M + 3]+, 430 (2.11) [M + 2]+, 429 (0.60) [M
+ 1]+, 428 (1.79) [M]+. HRMS (EI): calcd. for C20H14BrClN2O2
[M]+ 427.9927; found 427.9931.
Typical Reaction Procedure for the Phosphane-Mediated [2+1] An-
nulation: PBu3 (0.3 mmol) was added under argon to a mixture of
an acyl cyanide 1 (0.3 mmol) and ethyl (E)-2-cyano-3-phenylacryl-
ate (4, 0.3 mmol) in solvent and the reaction mixture was stirred at
reflux for the required time as indicated in the tables. After the
reaction solution had been concentrated under reduced pressure,
the residue was purified by flash chromatography on silica gel (elu-
ent: EtOAc/petroleum ether 1:8–1:4) to afford the pure product 5.
Ethyl 3-(4-Bromophenyl)-2-(4-chlorophenyl)-1,2-dicyanocycloprop-
anecarboxylate (5cЈ): M.p. 121–123 °C. 1H NMR (CDCl3,
400 MHz, TMS): δ = 1.18 (t, J = 7.2 Hz, 3 H, CH3), 4.05 (s, 1 H,
CH), 4.13 (qd, J1 = 1.2, J2 = 7.2 Hz, 2 H, CH2), 7.39–7.46 (m, 6
H, Ar), 7.64 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3,
Ethyl
2-(4-Chlorophenyl)-1,2-dicyano-3-phenylcyclopropanecarb-
oxylate (5a): M.p. 157–159 °C. 1H NMR (CDCl3, 400 MHz, TMS): 100 MHz): δ = 13.8, 34.2, 36.6, 37.2, 64.4, 112.7, 114.8, 124.1,
δ = 1.46 (t, J = 7.2 Hz, 3 H, CH3), 4.01 (s, 1 H, CH), 4.50 (q, J =
7.2 Hz, 2 H, CH2), 7.11 (d, J = 8.0 Hz, 2 H, Ar), 7.20 (d, J =
127.5, 127.7, 129.7, 130.3, 130.7, 132.6, 136.8, 161.1 ppm. IR
(CH Cl ): ν = 2983, 2960, 2926, 2246, 1745, 1595, 1492, 1013 cm–1.
˜
2
2
8.4 Hz, 2 H, Ar), 7.28–7.40 (m, 5 H, Ar) ppm. 13C NMR (CDCl3, MS (EI): m/z = 432 (1.31) [M + 4]+, 431 (0.85) [M + 3]+, 430 (3.10)
1986
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 1977–1988

Probing Phosphane-Mediated [2+1] Annulation Reactions
[M + 2]+, 429 (0.54) [M + 1]+, 428 (2.43) [M]+. HRMS (EI): calcd.
for C20H14BrClN2O2 [M]+ 427.9927; found 427.9922.
129.1, 129.2, 129.3, 129.4, 132.0, 139.1, 161.5 ppm. IR (CH Cl ): ν
˜
2 2
= 2984, 2922, 2870, 2245, 1751, 1608, 1501, 1449 cm–1. MS (EI):
m/z = 344 (21.51) [M]+. HRMS (EI): calcd. for C22H20N2O2 [M]+
344.1525; found 344.1527.
Ethyl
2-(4-Chlorophenyl)-1,2-dicyano-3-p-tolylcyclopropanecarb-
oxylate (5d): M.p. 161–163 °C. 1H NMR (CDCl3, 400 MHz, TMS):
δ = 1.46 (t, J = 7.2 Hz, 3 H, CH3), 2.33 (s, 3 H, CH3), 3.97 (s, 1
H, CH), 4.49 (q, J = 7.2 Hz, 2 H, CH2), 6.97 (d, J = 8.4 Hz, 2 H,
Ar), 7.11 (d, J = 8.4 Hz, 2 H, Ar), 7.21 (d, J = 8.8 Hz, 2 H, Ar),
7.35 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz):
δ = 14.0, 21.1, 32.4, 33.3, 40.9, 64.8, 112.6, 116.4, 124.4, 125.3,
Ethyl 2-(4-Chlorophenyl)-1,2-dicyano-3-(pyridin-3-yl)cyclopropane-
1
carboxylate (5g): H NMR (CDCl3, 400 MHz, TMS): δ = 1.47 (t,
J = 7.2 Hz, 3 H, CH3), 4.01 (s, 1 H, CH), 4.52 (q, J = 7.2 Hz, 2
H, CH2), 7.08 (dt, J1 = 2.0, J2 = 8.4 Hz, 1 H, Ar), 7.17 (dd, J1 =
4.8, J2 = 8.4 Hz, 1 H, Ar), 7.23 (d, J = 8.8 Hz, 2 H, Ar), 7.40 (d, J
= 8.8 Hz, 2 H, Ar), 8.60–8.62 (m, 2 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz): δ = 14.0, 32.4, 33.1, 38.3, 65.2, 112.1, 115.8, 123.0,
124.4, 124.5, 130.0, 132.2, 135.8, 137.2, 150.5, 151.6, 162.5 ppm.
129.4, 129.5, 129.6, 132.2, 136.6, 139.5, 163.0 ppm. IR (CH Cl ): ν
˜
2
2
= 2984, 2925, 2239, 1746, 1518, 1493, 1240 cm–1. MS (EI): m/z =
310 (68.99) [M – 54]+. C21H17ClN2O2 (364.0979): calcd. C 69.14,
H 4.70, Cl 9.72, N 7.68, O 8.77; found C 69.35, H 5.00, N 7.69.
IR (CH Cl ): ν = 3091, 3034, 2986, 2939, 2241, 1747, 1594, 1574,
˜
2
2
1488, 1287, 1014 cm–1. MS (EI): m/z = 353 (16.90) [M + 2]+, 352
(62.33) [M + 1]+, 351 (6.37) [M]+. HRMS (EI): calcd. for
C19H14ClN3O2 [M]+ 351.0775; found 351.0778.
Ethyl
2-(4-Chlorophenyl)-1,2-dicyano-3-p-tolylcyclopropanecarb-
oxylate (5dЈ): M.p. 148–150 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 1.17 (t, J = 7.2 Hz, 3 H, CH3), 2.39 (s, 3 H, CH3), 4.08
(s, 1 H, CH), 4.12 (qd, J1 = 1.6, J2 = 7.2 Hz, 2 H, CH2), 7.30 (d,
J = 8.0 Hz, 2 H, Ar), 7.41–7.42 (m, 4 H, Ar), 7.45 (d, J = 8.0 Hz,
2 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.8, 21.2, 34.3,
36.7, 37.8, 64.2, 113.0, 115.1, 125.6, 128.0, 128.8, 129.6, 130.0,
Ethyl 2-(4-Chlorophenyl)-1,2-dicyano-3-(pyridin-3-yl)cyclopropane-
1
carboxylate (5gЈ): M.p. 146–148 °C. H NMR (CDCl3, 400 MHz,
TMS): δ = 1.19 (t, J = 7.6 Hz, 3 H, CH3), 4.09 (s, 1 H, CH), 4.12–
4.18 (m, 2 H, CH2), 7.41–7.48 (m, 5 H, Ar), 7.96–8.00 (m, 1 H,
Ar), 8.73 (dd, J1 = 1.2, J2 = 4.8 Hz, 1 H, Ar), 8.83 (d, J = 2.4 Hz,
1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.8, 34.0, 35.2,
36.3, 64.6, 112.5, 114.5, 123.9, 125.2, 127.2, 129.8, 130.3, 135.9,
130.4, 136.6, 139.6, 161.4 ppm. IR (CH Cl ): ν = 2963, 2926, 2856,
˜
2
2
2246, 1745, 1518, 1492, 1095 cm–1. MS (EI): m/z = 310 (70.08) [M –
54]+. C21H17ClN2O2 (364.0979): calcd. C 69.14, H 4.70, Cl 9.72, N
7.68, O 8.77; found C 69.18, H 5.02, N 7.68.
137.0, 150.7, 150.8, 160.9 ppm. IR (CH Cl ): ν = 2985, 2938, 2247,
˜
2
2
1746, 1595, 1573, 1484, 1248, 1016 cm–1. MS (EI): m/z = 353 (1.16)
[M + 2]+, 352 (2.14) [M + 1]+, 351 (2.84) [M]+. C19H14ClN3O2
(351.0775): calcd. C 64.87, H 4.01, Cl 10.08, N 11.94, O 9.10; found
C 64.81, H 4.10, N 12.13.
Ethyl 1,2-Dicyano-2,3-diphenylcyclopropanecarboxylate (5e): M.p.
1
115–117 °C. H NMR (CDCl3, 400 MHz, TMS): δ = 1.46 (t, J =
7.2 Hz, 3 H, CH3), 4.00 (s, 1 H, CH), 4.50 (qd, J1 = 0.8, J2
=
7.2 Hz, 2 H, CH2), 7.07–7.10 (m, 2 H, Ar), 7.25–7.30 (m, 4 H, Ar),
7.32–7.39 (m, 3 H, Ar), 7.40–7.45 (m, 1 H, Ar) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 14.0, 33.3, 40.9, 64.8, 112.7, 116.7, 126.6,
128.0, 128.5, 129.1, 129.2, 129.8, 130.2, 130.8, 163.2 ppm. IR
Ethyl 3-(4-Bromophenyl)-1,2-dicyano-2-(thiophen-3-yl)cyclopropane-
carboxylate (5h): M.p. 132–134 °C. 1H NMR (CDCl3, 400 MHz,
TMS): δ = 1.45 (t, J = 7.2 Hz, 3 H, CH3), 4.02 (s, 1 H, CH), 4.43–
4.54 (m, 2 H, CH2), 6.83 (dd, J1 = 1.6, J2 = 5.2 Hz, 1 H, Ar), 7.10
(d, J = 8.4 Hz, 2 H, Ar), 7.24 (dd, J1 = 1.6, J2 = 3.2 Hz, 1 H, Ar),
7.31 (dd, J1 = 3.2, J2 = 5.2 Hz, 1 H, Ar), 7.49 (d, J = 8.4 Hz, 2 H,
Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 14.0, 30.6, 33.9, 40.0,
64.9, 112.6, 116.1, 123.7, 126.1, 126.80, 126.82, 127.9, 128.2, 131.2,
(CH Cl ): ν = 3062, 3033, 2984, 2929, 2238, 1746, 1500, 1449,
˜
2
2
1238 cm–1. MS (EI): m/z
=
316 (2.40) [M]+. C20H16N2O2
(316.1212): calcd. C 75.93, H 5.10, N 8.86, O 10.11; found C 75.91,
H 5.14, N 8.82.
Ethyl 1,2-Dicyano-2,3-diphenylcyclopropanecarboxylate (5eЈ): M.p.
132.1, 162.7 ppm. IR (CH Cl ): ν = 3019, 2985, 2936, 2245, 1745,
˜
2
2
1
1491, 1282, 1011 cm–1. MS (EI): m/z = 402 (7.91) [M + 2]+, 400
(7.42) [M]+. C18H13BrN2O2S (399.9881): calcd. C 53.88, H 3.27, Br
19.91, N 6.98, O 7.97, S 7.99; found C 54.02, H 3.28, N 6.96.
158–160 °C. H NMR (CDCl3, 400 MHz, TMS): δ = 1.11 (t, J =
7.2 Hz, 3 H, CH3), 4.02–4.14 (m, 2 H, CH2), 4.16 (s, 1 H, CH),
7.42–7.52 (m, 8 H, Ar), 7.58–7.61 (m, 2 H, Ar) ppm. 13C NMR
(CDCl3, 100 MHz): δ = 13.7, 34.2, 37.3, 37.7, 64.0, 113.2, 115.3,
Ethyl 3-(4-Bromophenyl)-1,2-dicyano-2-(thiophen-3-yl)cyclopropane-
129.1, 129.2, 129.3, 129.4, 130.4, 161.4 ppm. IR (CH Cl ): ν =
˜
2
2
1
carboxylate (5hЈ): M.p. 152–154 °C. H NMR (CDCl3, 400 MHz,
3063, 3032, 2985, 2926, 2246, 1745, 1497, 1450, 1003 cm–1. MS
(EI): m/z = 316 (2.06) [M]+. C20H16N2O2 (316.1212): calcd. C
75.93, H 5.10, N 8.86, O 10.11; found C 76.00, H 5.06, N 8.82.
TMS): δ = 1.14 (t, J = 7.2 Hz, 3 H, CH3), 4.07 (s, 1 H, CH), 4.08–
4.19 (m, 2 H, CH2), 7.18 (dd, J1 = 1.6, J2 = 5.2 Hz, 1 H, Ar), 7.41
(dd, J1 = 3.2, J2 = 5.2 Hz, 1 H, Ar), 7.43 (d, J = 8.4 Hz, 2 H, Ar),
7.50 (dd, J1 = 1.6, J2 = 3.2 Hz, 1 H, Ar), 7.62 (d, J = 8.4 Hz, 2 H,
Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.7, 32.7, 34.7, 37.5,
64.2, 112.9, 114.7, 123.9, 127.1, 127.3, 127.7, 127.9, 128.6, 130.7,
Ethyl
1,2-Dicyano-2-(3,5-dimethylphenyl)-3-phenylcyclopropane-
1
carboxylate (5f): Liquid. H NMR (CDCl3, 400 MHz, TMS): δ =
1.46 (t, J = 7.2 Hz, 3 H, CH3), 2.24 (s, 6 H, CH3), 3.95 (s, 1 H,
CH), 4.49 (q, J = 7.2 Hz, 2 H, CH2), 6.85 (s, 2 H, Ar), 7.03 (s, 1
H, Ar), 7.09 (d, J = 7.2 Hz, 2 H, Ar), 7.25–7.29 (m, 2 H, Ar), 7.32–
7.36 (m, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 14.1,
21.1, 33.3, 41.0, 64.7, 112.7, 116.9, 126.2, 128.2, 128.3, 128.5, 129.1,
132.6, 160.9 ppm. IR (CH Cl ): ν = 3107, 2983, 2928, 2245, 1745,
˜
2
2
1493, 1010 cm–1. MS (EI): m/z = 402 (6.63) [M + 2]+, 400 (6.28)
[M]+. C18H13BrN2O2S (399.9881): calcd. C 53.88, H 3.27, Br 19.91,
N 6.98, O 7.97, S 7.99; found C 53.97, H 3.32, N 6.93.
129.9, 131.8, 139.0, 163.3 ppm. IR (CH Cl ): ν = 2984, 2922, 2870,
˜
2
2
Ethyl 3-(4-Bromophenyl)-1,2-dicyano-2-(naphthalen-1-yl)cycloprop-
anecarboxylate (5i): M.p. 203–205 °C. 1H NMR (CDCl3,
400 MHz, TMS): δ = 1.51 (t, J = 7.6 Hz, 3 H, CH3), 4.13 (s, 1 H,
CH), 4.50–4.64 (m, 2 H, CH2), 6.77–6.88 (m, 2 H, Ar), 7.22–7.29
2239, 1746, 1607, 1500, 1036 cm–1. MS (EI): m/z = 344 (19.70)
[M]+. HRMS (EI): calcd. for C22H20N2O2 [M]+ 344.1525; found
344.1520.
Ethyl
1,2-Dicyano-2-(3,5-dimethylphenyl)-3-phenylcyclopropane- (m, 2 H, Ar), 7.41–7.82 (m, 5 H, Ar), 7.89 (d, J = 7.6 Hz, 1 H, Ar),
carboxylate (5fЈ): M.p. 136–138 °C. 1H NMR (CDCl3, 400 MHz, 7.98 (d, J = 8.4 Hz, 1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ
TMS): δ = 1.13 (t, J = 7.2 Hz, 3 H, CH3), 2.33 (s, 6 H, CH3), 4.04– = 14.2, 30.3, 31.9, 40.7, 65.1, 112.6, 116.2, 122.0, 123.2, 123.6,
4.20 (m, 3 H, CH), 7.05 (s, 1 H, Ar), 7.06 (s, 2 H, Ar), 7.42–7.52
(m, 3 H, Ar), 7.57–7.60 (m, 2 H, Ar) ppm. 13C NMR (CDCl3,
100 MHz): δ = 13.8, 21.1, 34.0, 37.3, 37.8, 63.9, 113.3, 115.5, 126.7,
125.0, 126.8, 127.5, 127.6, 129.2, 130.4, 130.5, 131.0, 131.5, 131.7,
134.0, 163.0 ppm. IR (CH Cl ): ν = 3061, 2983, 2928, 2237, 1746,
˜
2
2
1595, 1493, 1260, 1011 cm–1. MS (EI): m/z = 446 (15.32) [M +
Eur. J. Org. Chem. 2010, 1977–1988
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1987

X.-G. Liu, Y. Wei, M. Shi
FULL PAPER
2]+, 445 (8.44) [M + 1]+, 444 (15.93) [M]+. C24H17BrN2O2
(444.0473): calcd. C 64.73, H 3.85, Br 17.94, N 6.29, O 7.19; found
C 64.68, H 3.91, N 6.22.
Chem. Int. Ed. 2007, 46, 4614–4628; f) Y. L. Shi, M. Shi, Eur.
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Ethyl 3-(4-Bromophenyl)-1,2-dicyano-2-(naphthalen-1-yl)cycloprop-
anecarboxylate (5iЈ): M.p. 249–251 °C. 1H NMR (CDCl3,
400 MHz, TMS): δ = 0.73–0.74 (m, 3 H, CH3), 3.72–3.81 (m, 2 H,
CH2), 4.18 (s, 1 H, CH), 7.49–7.72 (m, 8 H, Ar), 7.94 (d, J =
8.0 Hz, 1 H, Ar), 7.97 (d, J = 8.4 Hz, 1 H, Ar), 8.14 (d, J = 7.2 Hz,
1 H, Ar) ppm. 13C NMR (CDCl3, 100 MHz): δ = 13.2, 33.8, 36.3,
38.5, 64.0, 113.2, 114.8, 122.8, 124.0, 125.2, 125.6, 126.9, 127.9,
128.3, 128.6, 128.7, 129.3, 130.8, 131.5, 132.7, 133.8, 161.3 ppm.
IR (CH Cl ): ν = 3015, 2982, 2249, 1741, 1593, 1489, 1311,
˜
2
2
1011 cm–1. MS (EI): m/z = 446 (17.52) [M + 2]+, 445 (10.18) [M +
1]+, 444 (17.98) [M]+. C24H17BrN2O2 (444.0473): calcd. C 64.73, H
3.85, Br 17.94, N 6.29, O 7.19; found C 64.81, H 3.74, N 6.27.
Supporting Information (see also the footnote on the first page of
this article): NMR spectra of new compounds shown in tables and
schemes.
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Acknowledgments
We thank the Shanghai Municipal Committee of Science and Tech-
nology (06XD14005, 08dj1400100–2), the National Basic Research
Program of China (973)-2009CB825300, and the National Natural
Science Foundation of China (20472096, 20872162, 20672127,
20821002 and 20732008) for financial support and Mr. Jie Sun for
performing X-ray diffraction.
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[18] CCDC-714983 (for 3aЈ), -735020 (for 5a), -743550 (for 5cЈ),
and -719285 (for 8) contain the supplementary crystallographic
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from The Cambridge Crystallographic Data Centre via
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Received: October 30, 2009
Published Online: February 18, 2010
1988
www.eurjoc.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2010, 1977–1988