Cp?Rh(III)-Catalyzed Low Temperature C-H Allylation of N-Aryl-trichloro Acetimidamide

Article abstract of DOI:10.1021/acs.joc.6b02150

The readily synthesized trichloro acetimidamide was found to be an excellent directing group for the directed C-H-allylation reactions. Depending on the allylating agent used, selectively either mono- or diallylated products were readily synthesized. More

Full text of DOI:10.1021/acs.joc.6b02150

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Article
Cp*Rh(III)-Catalyzed Low Temperature C-
H Allylation of N-Aryl-trichloro Acetimidamide
Suvankar Debbarma, Sourav Sekhar Bera, and Modhu Sudan Maji
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.6b02150 • Publication Date (Web): 04 Nov 2016
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Cp*Rh(III)-Catalyzed Low Temperature C-H Allylation of N-Aryl-
trichloro Acetimidamide
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Suvankar Debbarma, Sourav Sekhar Bera, Modhu Sudan Maji*
Department of Chemistry, Indian Institute of Technology Kharagpur, Kharagpur 721302, India
ABSTRACT: The readily synthesized trichloro acetimidamide
was found to be an excellent directing group for the directed C-
H-allylation reactions. Depending on the allylating agent used,
selectively either mono- or di-allylated products were readily
synthesized. Moreover, the trichloro acetimidamide directing
group was found to be highly efficient even at lower temper-
ature for the C-H-allylation reaction. Due to mildness of the re-
action conditions, double bond isomerization or cyclization to
indole side product was not observed.
Scheme 1. Trichloroacetimidamide directed C-H allylation
INTRODUCTION
Recently transition-metal-catalyzed C-H-bond functionaliza-
tion has emerged as powerful methodology in organic synthe-
sis.1 Among many transition metal catalysts employed, Rh(III)-
has played a key role in this area. Using appropriate directing
group, many Rh(III)-catalyzed versatile reactions, such as C-H
allylation, alkenylation, amination, insertion to a C-C multiple
bond, etc. have been well documented in the literature.2 How-
ever these reactions are generally conducted at higher tempera-
ture. Despite numerous reactions reported in the literature, cor-
responding low temperature version is scarce.3 Finding a direct-
ing group which can work at lower temperature under mild re-
action conditions is highly desirable especially considering
functional group tolerability of substrates, and its application
for the asymmetric C-H bond functionalization.
Allylarenes, including 2-allyl aniline derivatives, are im-
portant starting materials considering its diverse applicability.4
Besides this, many natural products and biologically active
molecules contain allyl- and prenylarene moiety.5 It is generally
introduced by N-allylation reaction using a three step protocol
followed by amino Claisen reaction at very high temperature
(140 oC to 180 oC).6 At such a high temperature product decom-
position or undesired further rearrangement may take place.7
Hence C-H allylation of aniline derivatives under mild condi-
tions is an alternative and fruitful method to the amino-Claisen
reaction. N. Cramer et al. reported directed Rh(I)-catalyzed al-
lylation/ cyclization sequence of ketimine by insertion of C-H
bond to allene.8 S. Ma et al. reported a Cp*Rh(III)-catalyzed C-
electrophile has also been reported by X. Li et al.13 Alkene
isomerization was also
a significant side reaction for
Cp*Rh(III)-catalyzed allylation of N-sulfonyl ketimine by Q.
Ouyang and Y. Wei.14 High temperature Cp*Rh(III)-catalyzed
C-H-allylation of acetanilides furnished indoles directly leaving
no allylated products (Scheme 1b).15 Our attempt to synthesize
2-allyl-acetanilides at lower temperature using the same meth-
odology was not successful.15a In addition, unstoppable double
bond isomerization of the allylated products at higher tempera-
ture complicates the reaction profile, therefore product purifi-
cation becomes difficult.10a, 12, 14 Hence we intended to develop
a step- and atom-economic C-H-allylation method of aniline de-
rivatives at ambient or even at lower temperature to address the
above mentioned difficulties.
H
allylation of methoxybenzamides with allenes.9 In
Cp*Rh(III)-catalyzed C-H allylation of amide by F. Glorius et
al., double bond isomerization was significant side reaction.10
H. Wang et al. reported a C-H-allylation/ N-allylation sequence
by using Cp*Rh(III)/ Pd(II)-catalysis sequence.3c, 11 T.-P. Loh
et al. reported a Cp*Rh(III)-catalyzed allylation/ isomerization
sequence to synthesize 2-alkenylated amide products.12
Cp*Rh(III)-catalyzed C-H-allylation by using vinyloxirane
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RESULT AND DISCUSSION
absence only trace amount of 3a was detected (entry 5). Other
1
Cu(II)-salts additives such as cupric chloride and anhydrous
Cu(II)-acetate also did not provide better results (entries 6 and
7). Reducing the catalyst loading to 2.5 mol %, decreases the
yields of 3a to 52%, however 4a only detected in trace amount
(entry 8). Initially we anticipated 5a to be the more reactive
electrophilic allylating agent in comparison to allyl carbonate
5b as trichloroacetamide is known to be superior leaving group.
However, on changing the allylating agent from 5a to 5b, the
reaction time drastically reduced, and from the commencement
of the reaction both 3a and 4a products started to form in paral-
lel which made it difficult to synthesize 3a selectively over 4a
by using 5b (entry 9). On decreasing the catalyst loading to 3.0
mol %, similar results were obtained (entry 10). Interestingly
for this reaction Cu(OAc)2·H2O has no or little role on the out-
come of the reaction (entry 11).20 On prolonging the reaction
time to 7 h, diallylated product 4a was isolated exclusively in
74% yield (entry 12). For monoallylation reaction conditions
found under entry 4 using 5a, and for diallylation reaction con-
ditions found under entry 12 using 5b are our optimized reac-
tion conditions to check scope of these reactions.
To achieve C-H-allylation reaction, we have chosen trichloro
acetimidamide present in N-aryl-trichloro acetimidamide 1 as
our directing group for C-H allylation. We envisioned that the
C(sp2)–H bond can undergo cyclo-metalation to form six-mem-
bered rhoda-cycle 2 which might be our nucleophile for C-H
bond functionalization reaction.16 Due to strong electron with-
drawing nature of trichloromethyl moiety, it should facilitate
catalyst turnover in the catalytic cycle by easy release of cata-
lyst from imidamide units (Scheme 1d).17 It is noteworthy that
installation of trichloro acetimidamide group on aniline deriva-
tives is very straight forward, and just works by stirring anilines
or its derivatives with readily available and cheap trichloroace-
tonitrile at room temperature,18 which makes this directing
group even more viable and attractive.
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Table 1. Optimization of the reaction conditionsa
Scheme 2. Scope of the mono-allylation reactiona
entry 5a or cat
5b [mol %]
additives Cu(II)-salt timeyield [%]b
[h] 3a 4a
5a
5a
5a
5a
5a
5a
5a
5a
5
0
KPF6 Cu(OAc)2·H2O 36 41 ND
1
2
3
4
5
6
7
8
No
No
Cu(OAc)2·H2O 24
0
0
0
5
Cu(OAc)2·H2O 36 <2
5
AgSbF6 Cu(OAc)2·H2O 24 64 15
5
AgSbF6
AgSbF6
AgSbF6
--
36 <2
36 ND
36 trace
0
0
0
5
CuCl2
5
Cu(OAc)2
2.5
AgSbF6 Cu(OAc)2·H2O 24 52 tra
ce
5b
5b
5b
5b
5
3
3
3
AgSbF6 Cu(OAc)2·H2O 3 30 55
AgSbF6 Cu(OAc)2·H2O 3 34 50
9
10
11
12
AgSbF6
AgSbF6
--
--
3
7
34 55
74
0
aReaction conditions: 1a (0.1 mmol), 5a or 5b (0.25 mmol), [Cp*RhCl2]2
(2.5 to 5.0 mol %), additive (20 mol %), Cu(OAc)2·H2O (0 or 1.0 equiv),
DCE (0.5 mL), rt. bIsolated yields are reported. Condition: A (entry 4), Con-
dition: B (entry 11), Condition: C (entry 12).
We started optimization of the reaction conditions by using
allyl-2,2,2-trichloroacetimidate 5a as our allylating agent. After
screening several solvents, 1,2-dichloroethane (DCE) was
found to be the best solvent.19 We were delighted to isolate 41%
of monoallylated product 3a exclusively by using 5 mol % of
catalyst loading, 20 mol % of KPF6, and 1.0 equiv of
Cu(OAc)2·H2O as additives (table 1, entry 1). On conducting
the reactions by either omitting both catalyst and additive (entry
2) or only additive KPF6 (entry 3), either none or trace amount
of the product 3a were detected. Among several other Ag(I)-
additives tested to generate cationic Cp*Rh(III)-species,19
AgSbF6 provided the best results as 64% of 3a was isolated
along with 15% of diallylated product 4a (entry 4).
Cu(OAc)2·H2O is a mandatory additive for this reaction as in its
aIn parenthesis the ratio between 3 and 4 are given. b1-Methyl-allyl car-
c
bonate was used. 1,1-dimethyl-allyl carbonate was used. Although prod-
ucts 3 and 4 were isolated separately by column chromatography, combined
yields are reported. For conditions A and B, see table 1.
After optimizing the reaction conditions, we first studied the
scope of the monoallylation reaction with several N-aryl-tri-
chloro acetimidamide 1 and allylating agent 5a (Scheme 2). To
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compare the selectivity between the allylating agents, two reac- After successfully completing the scope of monoallylation
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tions were conducted in parallel by using 5a and 5b.
reaction, we further studied the scope of the diallylation reac-
tion by using 5b (Scheme 3). 2,6-Diallylated product 4a was
isolated in very high yield from unsubstituted aniline derivative
1a. 1b and 1p also reacted smoothly to provide 4b and 4p in
69% and 42% yields, respectively. 4-Chloro, 4-bromo, and 4-
iodo-aniline derived substrates also provided 4d, 4q, and 4e in
72 to 77% yields. Diallylated products 4f, 4g and 4j having
methoxy and phenyl functionalities on the aromatic ring were
also isolated in good yields (42-70%).
Scheme 3. Scope of the di-allylation reaction
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Figure 1. Unreacted allyl carbonate
Next we studied the reactivity of trichloro acetimidamide di-
recting group at lower temperature considering its potential and
applicability towards asymmetric C-H-bond functionalization
(Scheme 4).3,16 For substrate 1a, as discussed during optimiza-
tion (Table 1), both 3a and 4a started to form in parallel even at
lower temperature. However, on increasing the catalyst loading
As already discussed under optimization, 3a was synthesized
selectively by using 5a in 64% yield. Whereas allyl carbonate
5b provided mixture of products in 89% combined yields. For
p-toludine derivative 1b, moderate complimentary selectivity
was found for these two allylating agents and 3b and 4b were
isolated with excellent combined yields (90-94%). For substrate
1c, only monoallylated product 3c was isolated in 48-58%
yields. Again for 4-chloro-substituted substrate 1d, a reversal of
selectivity (3.5:1 versus 1:4.5) was found for these two allylat-
ing agents. Only allylating agent 5a provided 57% of monoal-
lylated product 3e for substrate 1e along with 28% of diallylated
product 4e. In sharp contrast for allylating agent 5b, diallylated
product 4e was sole product. In a similar way monoallylated
products 3f and 3g were synthesized selectively from substrates
1f and 1g by using 5a in excellent overall yields. Electron do-
nating 3-substituted aniline derivatives 1h-1i also reacted
smoothly by using allylating agent 5a, and products 3h-3i were
isolated in good yields with excellent selectivity (59-77%).
Again for substrate 1i, 5a was more selective for monoallylation
than allylating agent 5b. However, 5a failed to react with the
substrate 1j. Substrates 1k-1l having electron withdrawing
groups at the meta-position of the aryl moiety also underwent
smooth reaction with both the allylating agents to provide 3k
and 3l in 53 to 72% yields. For substrates 1h-1l, generally dial-
lylation product is suppressed due to steric reason. Finally, sub-
strates 1m-1o having methyl and fluorine substitution at the or-
tho-position, reacted smoothly with both allylating agents, and
provide 3m-3o with excellent yields (72-89% yields). To our
surprise, substrates 1p and 1q did not provide desired allylated
product 3p and 3q by using 5a. 1-Methyl-allyl carbonate also
reacted with 1a to provide product 3r with 69% yields. Pleas-
ingly valuable prenylated product 3s was isolated in 67% yield
under condition B by using 1,1-dimethylallyl carbonate. 2-Phe-
nylpyridine also reacted with 5a to provide mixture of 6 and its
diallylated product in 1.7:1 ratio (64%). As indicated in Scheme
2, widely used allylating agent 5b was not selective for mono
allylation (condition B), whereas 5a was very much selective
for the same (condition A). To our delight, in reference to the
previously reported allylation of aniline derivatives, no indole
or alkene isomerized products were detected under our reaction
conditions.10a, 12, 14-15
o
to 6 mol %, 4a was isolated in 90% yield at -20 C under the
identical reaction conditions. To our delight the allylated prod-
ucts 3i, 3k, and 3m-3o were isolated in 60-77% yields by using
o
5b at 0 C temperature. The outcome of the reaction did not
o
change much even when reactions were carried out at -20 C,
and products 3i, 3k and 3m-3o were isolated in 56-70% yields.
Scheme 4. C-H-Allylation reaction at lower temperature
aAt -20 oC 4a was isolated in 90% yield by using 6.0 mol % catalyst.
Finally, the imidamide 7 was reacted under the reaction con-
ditions C (table 1). Unlike 1b, only mono-allylated product 8
formed after prolonged reaction time indicating trichloro
acetimidamide is much reactive directing group in compared to
the corresponding phenyl acetimidamide (Scheme 5). As phe-
nylacetanilide did not provide any of the desired allylation prod-
uct, for substrate 9 having two amine moiety, we could selec-
tively synthesize 10 in 81% yield leaving other two C-H-bonds
intact. Finally, trichloro acetimidamide directed Fujiwara-
Moritani type alkenylation reaction was also successfully per-
formed by using 1a to provide product 11a. tert.-Butyl acrylate
also provided the desired alkenylated product 11b in 50% yield.
Amidine having ortho- and meta-methyl substitution also re-
acted smoothly to provide 11c and 11d in decent yields. Struc-
ture of 11a was confirmed by single crystal X-ray analysis.
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Scheme 5. Selective allylation of 9, alkenylation of 1a, and
ORTEP diagram of 11
ble C-H activation step in catalytic cycle. Intermolecular com-
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3
4
5
6
7
8
petition experiment using 1i and 1k showed that electron rich
amidine preferentially converted with almost 3:1 ratio (Scheme
6b), thus indicating C-H activation proceeds via intermolecular
electrophilic substitution (IES) pathway to provide intermediate
I.21a In addition, intermolecular competition experiment and
parallel experiment between 1a and [D5]-1a showing a kinetic
isotopic effect of around 2.0 and 1.9, respectively (Scheme 6c).
From all the above experiments it seems C-H bond cleavage
step is reversible and occurs before the rate determining steps
(RDS) of the overall process. As RDS is followed by the re-
versible C-H activation step, so little amount of KIE is ob-
served.21d
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To elaborate the mechanism, two possible pathways for the
subsequent C-C bond formation is proposed (Scheme 6d). The
coordination of the imidate oxygen to Rh(III) (II) probably fa-
cilitates an intramolecular substitution (pathway a).21b-c In path-
way b, olefin insertion of the allyl double bond into Rh-C bond
generates intermediate III with the imidate nitrogen chelating
to the metal. β-Rh-oxygen elimination delivers 3a and interme-
diate IV. We proposed that, in case of 5a, Cu(II)-played a cru-
cial role on releasing the active catalyst from the intermediate
IV by transmetallation to V.22 As for 5b Cu(II)-salt is not re-
quired, the trichloro acetimidamide directing group itself
doesn’t require any assistance from Cu(II)-salts as proved by
condition C.20
Scheme 6. Deuterium labelling study and proposed mecha-
nism
CONCLUSION
In conclusion, we have developed a mild allylation protocol for
the protected aniline derivatives. By this method either im-
portant 2-allyl- or 2,6-diallyl-anilines derivative can be synthe-
sized with excellent yields. The trichloromethyl functionality,
present in trichloro acetimidamide may tune the ligation ability,
and hence the catalyst turnover. We have also shown that read-
ily synthesize allyl trichloroimidate is a very selective allylating
agent. Our method doesn’t provide any side product related to
double bond isomerization or N─H insertion to allyl moiety.
Reaction can even be performed at lower temperature, and
hence this directing group is promising for the aniline function-
alization at lower temperature.
EXPERIMENTAL SECTION
General Procedure. All reactions were carried out in an oven dried
sealed tube under an inert atmosphere using standard Schlenk tech-
niques. Analytical thin layer chromatography (TLC) was per-
formed on pre-coated silica gel 60 F254 plates. Column chroma-
tography was performed through silica gel (100-200 mesh) using a
proper solvent system. Infrared (IR) spectra were recorded by FTIR
spectrometer and reported in cm-1. 1H NMR and 13C NMR are rec-
orded on a (400 MHz) and (600 MHz) spectrometer in CDCl3. 19
F
NMR were recorded in 400 MHz spectrometer in CDCl3. Data are
reported in the following order: chemical shift (δ) in ppm; multi-
plicities are indicated as br (broad), s (singlet), d (doublet), t (tri-
plet), q (quartet), m (multiplet); coupling constants (J) are given in
Hertz (Hz). Chemical shift for 1H NMR spectra were reported with
respect to the residual signal of CHCl3 at 7.26 ppm present in
CDCl3. Chemical shifts for 13C NMR spectra were mentioned in
ppm with respect to the center of a triplet at 77.16 ppm of chloro-
form-d. High resolution mass spectra (HRMS) were recorded by
using TOF, ESI (+ Ve) method. Other chemicals were obtained
from commercial sources, and were used without further purifica-
tion. Single crystal X-ray data of the crystal was collected at 293 K
on a CCD diffractometer.
To gain insight into the reaction mechanism, we conducted
experiments with isotopically labelled solvents with substrate
1a (Scheme 6a). We observed that combination of additives and
catalysts were essential for C-H/D exchange.19,21e Sufficient
amount of H/D scrambling in the product 1aʹ supports a reversi-
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General experimental section. General Procedure I (GP I):
Low Temperature C-H Allylation of 1 with 5b. N-Aryl-trichloro-
acetimidamide 1 (0.2 mmol, 1.0 equiv) was taken in a 12.0 mL
screw capped reaction tube, and 1.0 mL of anhydrous 1,2-dichlo-
roethane was added. Then catalyst [Cp*RhCl2]2 (4.0 mg, 0.006
mmol, 0.03 equiv) and AgSbF6 (13.7 mg, 20.0 mol %) were added
to the reaction mixture at room temperature, respectively. The re-
sultant reaction mixture was purged with argon gas and cooled
1
2
3
4
5
6
7
8
Synthesis of N-aryl-trichloroacetimidamide (1). Amidines 1a-q
and 10 were synthesized according to the literature reported proce-
dure.18 To a solution of amines (10.0 mmol) and ethanol (5.0 mL),
trichloroacetonitrile (12.0 mmol, 1.2 mL) was added at room tem-
perature. The resultant reaction mixture was allowed to stir at the
same temperature and monitored by TLC. Depending on substrate,
the reaction time varies from 3 to 5 days. Water was added to the
reaction mixture, which results precipitation of N-Aryl-trichloroa-
cetimidamide product 1a-q and 10. The isolated crude product was
purified by column chromatography by using 5 % ethylacetate in
hexane eluent.
o
down to -20 C. Finally, allylcarbonate 5b (0.5 mmol, 2.5 equiv)
was added at the same temperature and reaction was continued for
another 2 days at the same temperature. After completion of the
o
9
reaction as indicated by TLC, silica gel was added at -20 C and
immediately loaded on a silica gel column. The column was eluted
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with petroleum ether/ ethylacetate (98:2) to obtain pure product 3.
General Procedure II (GP II): Synthesis of allyl-2,2,2-trichloro-
acetimidate (5a). Allyl-2,2,2-trichloroacetimidate was prepared ac-
cording to the literature reported procedure.23 To a stirring mixture
of sodium hydride (1.5 mmol, 0.1 equiv) in dry ether, allylalcohol
(15.0 mmol, 1.0 equiv) was added, and the resulting mixture was
stirred under nitrogen atmosphere. Then the reaction mixture was
cooled down to -5 oC, trichloroacetonitrile (18.0 mmol, 1.2 equiv)
was added, and stirring was continued at the same temperature for
another 15 min. Finally, the reaction mixture was stirred at room
temperature for one hour. After completion of the reaction, solvent
was removed under reduced pressure, and the residual crude prod-
uct was extracted with n-pentane (3 x 15 mL). Pentane was re-
moved under reduced pressure to obtain the product 5a as colour-
less liquid, and used without further purification.
General Procedure D (GP D):C-H alkenylation with 1. N-Aryl-
trichloroacetimidamide 1 (0.2 mmol, 2.0 equiv) was taken in a 12.0
ml screw capped reaction tube, and 1.0 ml of anhydrous 1,2-dichlo-
roethane was added. Then ethyl acrylate (0.5 mmol, 2.5 equiv), cat-
alyst [Cp*RhCl2]2 (6.2 mg, 0.01 mmol, 5.0 mol %), AgSbF6 (13.7
mg, 0.04 mmol, 20 mol%) and Cu(OAc)2·H2O (79.8 mg, 0.4 mmol,
0.2 equiv) were added to the reaction mixture at room temperature
respectively. The resultant reaction mixture was purged with argon
gas and allowed to stir at the same temperature for 24 h. Then the
reaction mixture was purified on neutral silica gel column using
20% ethyl acetate in hexane as eluent.
2,2,2-trichloro-N-phenylacetimidamide
(1a).18
Prepared
according to the GP I and 1a was isolated as white solid (1.85 g,
1
General Procedure A (GP A): Monoallylation of 1 with 5a. N-
Aryl-trichloroacetimidamide 1 (0.2 mmol, 1.0 equiv) was taken in
a 12.0 mL screw capped reaction tube, and 1.0 mL of anhydrous
1,2-dichloroethane was added. Then allyl-2,2,2-trichloroacetimi-
date 5a (0.5 mmol, 2.5 equiv), catalyst [Cp*RhCl2]2 (6.2 mg, 0.01
mmol, 0.05 equiv), AgSbF6 (13.7 mg, 20.0 mol %), and
Cu(OAc)2.H2O (39.8 mg, 0.2 mmol, 1.0 equiv) were added to the
reaction mixture at room temperature, respectively. The resultant
reaction mixture was purged with argon gas, and allowed to stir at
the same temperature for 24 to 36 h depending on the substrate.
After completion of reaction as indicated by TLC, the reaction mix-
ture was filtered through a small pad of celite, and purified by col-
umn chromatography using petroleum ether/ ethylacetate (98:2) as
eluent.
78%). H NMR (600 MHz, CDCl3): δ (ppm): 7.37 (t, J = 7.9 Hz,
2H), 7.11 (t, J = 7.4 Hz, 1H), 6.92 (d, J = 7.6 Hz, 2H), 4.98 (br s,
2H). 13C NMR (150 MHz, CDCl3): δ (ppm) 152.8, 147.4, 129.8,
124.3, 120.5, 94.4.
2,2,2-trichloro-N-(2,3,4,5,6-penta
deuterio)acetimidamide
([D5]-1a). Prepared according to the GP I using aniline-d5 (in 1.2
mmol scale) and [D5]-1a was isolated as white solid (190 mg,
1
64%). IR (KBr): 3482, 3376, 1661, 1584, 1379, 1335 cm-1. H
NMR (400 MHz, CDCl3): δ (ppm) 4.99 (br s, 2H). 13C NMR (100
MHz, CDCl3): δ (ppm) 152.9, 147.4, 129.4 (t, J = 24.1 Hz), 123.9
(t, J = 24.1 Hz), 120.2 (t, J = 24.7 Hz), 94.5.
2,2,2-trichloro-N-p-tolylacetimidamide
(1b).18
Prepared
according to the GP I and 1b was isolated as white solid (1.41 g,
1
56%). H NMR (600 MHz, CDCl3): δ (ppm) 7.17 (d, J = 7.8 Hz,
General Procedure B (GP B): Monoallylation of 1 with 5b. N-
Aryl-trichloroacetimidamide 1 (0.2 mmol, 1.0 equiv) was taken in
a 12.0 mL screw capped reaction tube and 1.0 mL of anhydrous
1,2-dichloroethane was added. Then allylcarbonate 5b (0.5 mmol,
2.5 equiv), catalyst [Cp*RhCl2]2 (4.0 mg, 0.006 mmol, 0.03 equiv)
and AgSbF6 (13.7 mg, 20.0 mol %) were added to the reaction mix-
ture at room temperature, respectively. The resultant reaction mix-
ture was purged with argon gas and allowed to stir at the same tem-
perature for 2 to 3 h depending on the substrate. After completion
of the reaction as indicated by TLC, the crude product was directly
purified by column chromatography using petroleum ether/
ethylacetate (98:2) as eluent.
2H), 6.82 (d, J = 10.0 Hz, 2H), 4.98 (br s, 2H), 2.33 (s, 3H). 13C
NMR (150 MHz, CDCl3) δ 152.9, 144.9, 133.8, 130.4, 120.5, 94.6,
21.0. HRMS (ESI): calculated for C9H10Cl3N2 ([M+H]+): 250.9904;
found 250.9912.
2,2,2-trichloro-N-(4-fluorophenyl)acetimidamide (1c).Prepared
according to the GP I and 1c was isolated as brown solid (1.41 g,
o
55%). mp 124-126 C. IR (KBr): 3456, 3329, 1660, 1500, 1345,
1211 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.06 (t, J = 8.6
Hz, 2H), 6.89 (dd, J = 8.6, 4.9 Hz, 2H), 5.01 (br s, 2H). 13C NMR
(150 MHz, CDCl3): δ (ppm) 159.79 (d, J = 240 Hz), 153.38, 143.40
(d, J = 3.0 Hz), 122.03 (d, J = 7.5 Hz), 116.64 (d, J = 22.5 Hz),
94.36. 19F NMR (376 MHz, CDCl3): δ (ppm) -119.3 (s, 1F). HRMS
(ESI): calculated for C8H7Cl3FN2 ([M+H]+): 254.9653; found
254.9655.
General Procedure C (GP C): Diallylation of 1 with 5b. N-Aryl-
trichloroacetimidamide 1 (0.2 mmol, 1.0 equiv) was taken in a 12.0
mL screw capped reaction tube and 1.0 mL of anhydrous 1,2-di-
chloroethane was added. Then allylcarbonate 5b (0.5 mmol, 2.5
equiv), catalyst [Cp*RhCl2]2 (4.0 mg, 0.006 mmol, 0.03 equiv) and
AgSbF6 (13.7 mg, 20.0 mol %) were added to the reaction mixture
at room temperature, respectively. The resultant reaction mixture
was purged with argon gas, and allowed to stir at the same temper-
ature for 3 to 9 h depending on the substrate. After completion of
the reaction as indicated by TLC, the crude product was directly
purified by column chromatography using petroleum ether/
ethylacetate (98:2) as eluent.
2,2,2-trichloro-N-(4-chlorophenyl)acetimidamide (1d). repared
according to the GP I and 1d was isolated as yellow solid (1.36 g,
o
55%). mp 150-152 C. IR (KBr): 3478, 3372, 1681, 1581, 1483,
1090 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.34 (d, J = 8.6
Hz, 2H), 6.88 (d, J = 8.6 Hz, 2H), 5.01 (br s, 2H). 13C NMR (150
MHz, CDCl3): δ (ppm) 153.2, 146.1, 130.0, 129.7, 122.1, 94.3.
HRMS (ESI): calculated for C8H7Cl4N2 ([M+H]+): 270.9358;
found 270.9383.
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Page 6 of 10
2,2,2-trichloro-N-(4-iodophenyl)acetimidamide (1e). Prepared
(ppm) 156.51 (d, J = 252 Hz), 153.98, 143.54 (d, J = 3.0 Hz),
1
2
3
4
5
6
7
8
according to the GP I and 1e was isolated as yellow solid (1.89 g,
125.98 (d, J = 7.5 Hz), 121.53 (q, J = 271.8 Hz), 119.42 (d, J = 3
Hz), 118.43 (d, J = 21 Hz), 94.02. 19F NMR (376 MHz, CDCl3): δ
(ppm) -61.50 (d, J = 13.2 Hz, 3F), -120.69 – -120.79 (m, 1F).
HRMS (ESI): calculated for C9H6Cl3F4N2 ([M+H]+): 322.9527,
found 322.9525.
o
52%). mp 104-106 C. IR (KBr): 3483, 3382, 2923, 1663, 1584,
1
1477 cm-1. H NMR (600 MHz, CDCl3): δ (ppm) 7.68-7.66 (m,
2H), 6.72-6.69 (m, 2H), 5.01 (br s, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 153.1, 147.3, 138.9, 122.9, 94.2, 88.0. HRMS
(ESI): calculated for C8H7Cl3IN2 ([M+H]+): 362.8714; found
362.8718.
2,2,2-trichloro-N-o-tolylacetimidamide
(1m).18
Prepared
according to the GP I and 1m was isolated as black solid (1.31 g,
1
2,2,2-trichloro-N-(4-methoxyphenyl)acetimidamide (1f). epared
according to the GP I and 1f was isolated as brown solid (1.87 g,
70%). mp 74-76 oC. IR (KBr): 3420, 3332, 1661, 1502, 1236, 1014
cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 6.92-6.88 (m, 4H), 5.01
(br s, 2H), 3.79 (s, 3H). 13C NMR (150 MHz, CDCl3): δ (ppm)
156.5, 153.1, 140.4, 121.7, 115.1, 94.6, 55.6. HRMS (ESI): calcu-
lated for C9H10Cl3N2O ([M+H]+): 266.9853; found 266.9858.
52%). H NMR (600 MHz, CDCl3): δ (ppm) 7.21 (d, J = 7.5 Hz,
1H), 7.18 (t, J = 7.6 Hz, 1H), 7.02 (t, J = 7.4 Hz, 1H), 6.79 (d, J =
7.6 Hz, 1H), 4.89 (br s, 2H), 2.14 (s, 3H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.0, 145.7, 131.1, 129.0, 127.1, 124.3, 119.7,
94.3, 17.3. HRMS (ESI): calculated for C9H10Cl3N2 ([M+H]+):
250.9904; found 250.9911.
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18
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34
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60
2,2,2-trichloro-N-(2,3-dimethylphenyl)acetimidamide
(1n).
N-(biphenyl-4-yl)-2,2,2-trichloroacetimidamide (1g). Prepared
according to the GP I and 1g was isolated as white solid (1.69 g,
54%). mp 92-94 oC. IR (KBr): 3476, 3374, 1639, 1582, 1482, 1337
cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.62 (d, J = 8.4 Hz,
2H), 7.59 (d, J = 7.8 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.34 (t, J =
7.4 Hz, 1H), 7.02 (d, J = 8.3 Hz, 2H), 5.05 (br s, 2H). 13C NMR
(150 MHz, CDCl3): δ (ppm) 153.0, 146.8, 140.7, 137.3, 129.0,
128.5, 127.3, 127.0, 121.1, 94.5. HRMS (ESI): calculated for
C14H12Cl3N2 ([M+H]+): 313.0061; found 313.0062.
Prepared according to the GP I and 1n was isolated as white solid
(1.54 g, 60%). mp 130-132 oC. IR (KBr): 3471, 3364, 2918, 1657,
1577, 1468, 1333 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.08
(t, J = 7.6 Hz, 1H), 6.92 (d, J = 7.5 Hz, 1H), 6.67 (d, J = 7.8 Hz,
1H), 4.88 (br s, 2H), 2.29 (s, 3H), 2.06 (s, 3H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.0, 145.7, 138.4, 127.6, 126.5, 125.9, 117.4,
94.5, 20.4, 13.4. HRMS (ESI): calculated for C10H12Cl3N2
([M+H]+): 265.0061; found 265.0075.
2,2,2-trichloro-N-(2-fluorophenyl)acetimidamide (1o).Prepared
according to the GP I and 1o was isolated as sticky colorless solid
2,2,2-trichloro-N-(m-tolyl)acetimidamide (1h).18 Prepared
according to GP I and 1h was isolated as yellow solid (1.06, 42%).
1H NMR (600 MHz, CDCl3): δ (ppm) 7.27-7.25 (m, 1H), 6.93 (d,
J = 7.6 Hz, 1H), 6.76-6.73 (m, 2H), 4.98 (br s, 2H), 2.35 (s, 3H).
13C NMR (150 MHz, CDCl3): δ (ppm) 152.8, 147.5, 139.8, 129.7,
125.1, 121.2, 117.4, 94.5, 21.5. HRMS (ESI): calculated for
C9H10Cl3N2 ([M+H]+): 250.9904; found 250.9912.
o
(1.23 g, 48%). mp 72-74 C. IR (KBr): 3405, 3166, 2842, 1664,
1
1016 cm-1. H NMR (600 MHz, CDCl3): δ (ppm) 7.16-7.07 (m,
3H), 6.99 (t, J = 7.9 Hz, 1H), 5.09 (br s, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 153.75, 153.29 (d, J = 244.5 Hz), 134.60 (d, J =
12 Hz), 125.60 (d, J = 6.0 Hz), 125.12 (d, J = 4.5 Hz), 123.39 (d, J
= 1.5 Hz), 116.73 (d, J = 19.5 Hz), 94.06. 19F NMR (376 MHz,
CDCl3): δ (ppm) -130.4 (s, 1F). HRMS (ESI): calculated for
C8H7Cl3FN2 ([M+H]+): 254.9653; found 254.9659.
2,2,2-trichloro-N-(3-methoxyphenyl)acetimidamide (1i). epared
according to the GP I and 1i was isolated as yellow sticky solid
o
(1.15 g, 43%). mp 90-92 C. IR (KBr): 3454, 3342, 1671, 1592,
2,2,2-trichloro-N-(4-ethylphenyl)acetimidamide (1p). Prepared
according to the GP I and 1p was isolated as white solid (1.59 g,
1485, 1202 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.26 (t, J =
8.0 Hz, 1H), 6.66 (d, J = 8.1 Hz, 1H), 6.50 (d, J = 7.6 Hz, 1H), 6.47
(s, 1H), 5.04 (br s, 2H), 3.79 (s, 3H). 13C NMR (150 MHz, CDCl3):
δ (ppm) 161.0, 153.0, 148.9, 130.7, 112.6, 110.3, 106.2, 94.4, 55.4.
HRMS (ESI): calculated for C9H10Cl3N2O ([M+H]+): 266.9853;
found 266.9854.
o
60%). mp 124-126 C. IR (KBr): 3476, 3368, 2970, 1658, 1585,
1504, 1336 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.19 (d, J
= 8.1 Hz, 2H), 6.84 (d, J = 6.8 Hz, 2H), 5.00 (br s, 2H), 2.63 (q, J
= 7.6 Hz, 2H), 1.23 (t, J = 7.6 Hz, 3H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.9, 145.0, 140.2, 129.2, 120.5, 94.6, 28.4, 15.7.
HRMS (ESI): calculated for C10H12Cl3N2 ([M+H]+): 265.0061;
found 265.0063.
2,2,2-trichloro-N-(3,4-dimethoxyphenyl)acetimidamide
(1j).
Prepared according to the GP I and 1j was isolated as yellow solid
(1.77 g, 60%). mp 120-122 oC. IR (KBr): 3441, 3345, 1675, 1604,
1505, 1227 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 6.85 (d, J
= 8.4 Hz, 1H), 6.51 (d, J = 2.3 Hz, 1H), 6.47 (dd, J = 8.4, 2.3 Hz,
1H), 5.07 (br s, 2H), 3.86 (s, 6H). 13C NMR (150 MHz, CDCl3): δ
(ppm) 153.3, 150.1, 145.9, 140.9, 112.2, 111.6, 106.2, 94.6, 56.2,
56.0. HRMS (ESI): calculated for C10H12Cl3N2O2 ([M+H]+):
296.9959; found 296.9967.
2,2,2-trichloro-N-(4-bromophenyl)acetimidamide
(1q).
Prepared according to the GP I and 1q was isolated as white solid
(1.52 g, 48%). mp 128-130 oC. IR (KBr): 3486, 3385, 1667, 1584,
1481, 1330, 1239 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.48
(d, J = 8.6 Hz, 2H), 6.82 (d, J = 8.3 Hz, 2H), 5.01 (br s, 2H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 153.2, 146.6, 132.9, 122.5,
117.4, 94.2. HRMS (ESI): calculated for C8H7BrCl3N2 ([M+H]+):
314.8853; found 314.8869.
2,2,2-trichloro-N-(3-chlorophenyl)acetimidamide (1k). repared
according to the GP I and 1k was isolated as yellow solid (1.03 g,
38%). mp 76-78 oC. IR (KBr): 3439, 3326, 1661, 1585, 1466, 1352
cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.30 (t, J = 8.0 Hz, 1H),
δ 7.09 (d, J = 8.0 Hz, 1H), 6.94 (t, J = 1.8 Hz, 1H), 6.81 (d, J = 7.9
Hz, 1H), 5.04 (br s, 2H). 13C NMR (150 MHz, CDCl3): δ (ppm)
153.3, 148.8, 135.4, 131.0, 124.5, 120.9, 118.9, 94.2. HRMS (ESI):
calculated for C8H7Cl4N2 ([M+H]+): 270.9358; found 270.9382.
N-(2-allylphenyl)-2,2,2-trichloroacetimidamide (3a). The titled
compound 3a was prepared by following the GP A. The product 3a
was isolated as gummy solid (36 mg, 64%) and in a second fraction
product 4a was also isolated as sticky solid (9.5 mg, 15%). IR
(neat): 3477, 3371, 2928, 1660, 1579, 1481,856,785 cm-1. 1H NMR
(600 MHz, CDCl3): δ (ppm) 7.28 (d, J = 8.2 Hz, 1H), 7.25 (t, J =
7.6 Hz, 1H), 7.10 (t, J = 7.1 Hz, 1H), 6.85 (d, J = 7.7 Hz, 1H), 5.97-
5.90 (m, 1H), 5.09 (d, J = 17.0 Hz, 1H), 5.04 (d, J = 10.9 Hz, 1H),
4.94 (br s, 2H), 3.31 (d, J = 6.8 Hz, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.2, 145.4, 137.0, 131.9, 130.4, 127.6, 124.6,
119.8, 115.9, 94.5, 35.9. HRMS (ESI): calculated for C11H12Cl3N2
([M+H]+): 277.0061; found 277.0065.
2,2,2-trichloro-N-(4-fluoro-3-(trifluoromethyl)phenyl)
acetimidamide (1l). Prepared according to the GP I and 1l was
o
isolated as yellow solid (0.91 g, 28%). mp 152-154 C. IR (KBr):
1
3465, 3296, 3175, 1652, 1498, 1427, 1324 cm-1. H NMR (600
MHz, CDCl3): δ (ppm) 7.20 (t, J = 9.3 Hz, 1H), 7.16 (d, J = 3.7 Hz,
1H), 7.09 (s, 1H), 5.09 (br s, 2H). 13C NMR (150 MHz, CDCl3): δ
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The Journal of Organic Chemistry
2,2,2-trichloro-N-(2,6-diallylphenyl)acetimidamide (4a). The ti-
N-(2-allyl-4-iodophenyl)-2,2,2-trichloroacetimidamide
(3e).
1
2
3
4
5
6
7
8
tled compound 4a was prepared by following the GP C and isolated
The titled compound 3e was prepared by following the GP A. The
product 3e was isolated as sticky white solid (44 mg, 55%) and in
a second fraction product 4e was also isolated as white sticky solid
(27 mg, 30%). IR (neat): 3484, 3380, 2923, 2853, 1668, 1585,
1471, 830 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.57 (s, 1H),
7.53 (dd, J = 8.2, 1.8 Hz, 1H), 6.60 (d, J = 8.2 Hz, 1H), 5.89-5.82
(m, 1H), 5.11-5.04 (m, 2H), 4.94 (br s, 2H), 3.22 (d, J = 6.8 Hz,
2H). 13C NMR (150 MHz, CDCl3): δ (ppm) 152.4, 145.3, 139.2,
136.6, 136.1, 134.7, 122.0, 116.7, 94.2, 88.3, 35.5. HRMS (ESI):
calculated for C11H11Cl3IN2 ([M+H]+): 402.9027; found 402.9027.
as white sticky solid (47 mg, 74%). IR (neat): 3469, 3363, 2923,
1
1660, 1580, 1446, 912, 860 cm-1. H NMR (600 MHz, CDCl3): δ
(ppm) 7.11 (d, J = 7.6 Hz, 2H), 7.03 (t, J = 7.5 Hz, 1H), 5.95-5.88
(m, 2H), 5.09 (dd, J = 17.0, 1.4 Hz, 2H), 5.03 (d, J = 10.0 Hz, 2H),
4.83 (br s, 2H), 3.22 (qd, J = 15.2, 6.8 Hz, 4H). 13C NMR (150
MHz, CDCl3): δ (ppm) 151.5, 143.2, 137.0, 130.7, 128.2, 124.2,
116.1, 94.1, 35.7. HRMS (ESI): calculated for C14H16Cl3N2
([M+H]+): 317.0374; found 317.0376.
9
N-(2-allyl-4-methylphenyl)-2,2,2-trichloroacetimidamide (3b).
The titled compound 3b was prepared by following the GP A. The
product 3b was isolated as gummy solid (31.5 mg, 54%) and in a
second fraction product 4b was also isolated as white sticky solid
(24 mg, 36%). IR (neat): 3473, 3371, 2922, 2853, 1678, 1662,
1583, 1489, 908, 827 cm-1. 1H NMR (400 MHz, CDCl3) δ 7.06 (s,
1H), 7.03 (d, J = 7.9 Hz, 1H), 6.74 (d, J = 7.1 Hz, 1H), 5.95-5.85
(m, 1H), 5.09-5.00 (m, 2H), 4.93 (br s, 2H), 3.25 (d, J = 6.6 Hz,
2H), 2.31 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 152.5,
137.2, 134.1, 131.7, 131.1, 128.2, 119.83, 119.81, 115.8, 94.5,
36.0, 21.0. HRMS (ESI): calculated for C12H14Cl3N2 ([M+H]+):
291.0217; found 291.0228.
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2,2,2-trichloro-N-(2,6-diallyl-4-iodophenyl)acetimidamide (4e).
The titled compound 4e was prepared by following the GP C and
isolated as white sticky solid (64 mg, 72%). IR (neat): 3484, 3377,
1
3077, 2923, 2853, 1668, 1582, 918 cm-1. H NMR (600 MHz,
CDCl3): δ (ppm) 7.42 (s, 2H), 5.90-5.82 (m, 2H), 5.11-5.06 (m,
4H), 4.86 (br s, 2H), 3.20-3.10 (m, 4H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 151.8, 143.1, 136.9, 136.0, 133.3, 116.9, 93.9,
88.5, 35.3. HRMS (ESI): calculated for C14H15Cl3IN2 ([M+H]+):
442.9340; found 442.9353.
N-(2-allyl-4-methoxyphenyl)-2,2,2-trichloroacetimidamide (3f).
The titled compound 3f was prepared by following the GP A. The
product 3f was isolated as white gummy solid (46 mg, 75%) and in
a second fraction product 4f was also isolated (9 mg, 12%). IR
2,2,2-trichloro-N-(2,6-diallyl-4-methylphenyl)acetimidamide
(4b). The titled compound 4b was prepared by following the GP C
and isolated as white sticky solid (46 mg, 69%). IR (neat): 3441,
3308, 2919, 1643, 1583, 917, 848, 789 cm-1. 1H NMR (400 MHz,
CDCl3): δ (ppm) 6.91 (s, 2H), 5.95-5.85 (m, 2H), 5.08 (d, J = 17.1
Hz, 2H), 5.02 (d, J = 9.9 Hz, 2H), 4.82 (br s, 2H), 3.21-3.12 (m,
4H), 2.29 (s, 3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 151.7,
140.5, 137.1, 133.7, 130.4, 128.8, 115.9, 94.2, 35.8, 21.0. HRMS
(ESI): calculated for C15H18Cl3N2 ([M+H]+): 331.0530; found
331.0532.
1
(neat): 3478, 3371, 2931, 2838, 1665, 1604, 1491, 916 cm-1. H
NMR (600 MHz, CDCl3): δ (ppm) 6.82 (s, 1H), 6.77 (s, 2H), 5.93-
5.86 (m, 1H), 5.08 (ddd, J = 17.0, 3.2, 1.5 Hz, 1H), 5.02 (d, J = 9.9
Hz, 1H), 4.93 (br s, 2H), 3.79 (s, 3H), 3.26 (d, J = 6.6 Hz, 2H). 13
C
NMR (150 MHz, CDCl3): δ (ppm) 156.7, 152.6, 138.5, 136.8,
133.4, 120.6, 116.1, 115.9, 112.7, 94.6, 55.5, 36.1. HRMS (ESI):
calculated for C12H14Cl3N2O ([M+H]+): 307.0166; found
307.0175.
N-(2-allyl-4-fluorophenyl)-2,2,2-trichloroacetimidamide (3c).
The titled compound 3c was prepared by following the GP A and
isolated as white sticky solid (34.3 mg, 58%). IR (neat): 3490,
3390, 1661, 1485, 1219, 823, 787 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 6.98 (dd, J = 9.4, 2.5 Hz, 1H), 6.92 (td, J = 8.3,
2.6 Hz, 1H), 6.78 (s, 1H), 5.91-5.84 (m, 1H), 5.10-5.05 (m, 2H),
4.95 (br s, 2H), 3.26 (d, J = 6.6 Hz, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 159.96 (d, J = 241.5 Hz), 152.9, 141.2, 136.1,
134.15 (d, J = 3 Hz), 121.0, 117.02 (d, J = 22.5 Hz), 116.7, 114.22
(d, J = 22.5 Hz), 94.3, 35.8. 19F NMR (376 MHz, CDCl3): δ (ppm)
-126.8 (s, 1F). HRMS (ESI): calculated for C11H11Cl3FN2
([M+H]+): 294.9966; found 294.9953.
2,2,2-trichloro-N-(2,6-diallyl-4-methoxyphenyl)acetimidamide
(4f). The titled compound 4f was prepared by following the GP C
and isolated as white sticky solid (45 mg, 65%). IR (neat): 3476,
3368, 2936, 2836, 1663, 1464, 1146, 848 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 6.67 (s, 2H), 5.93-5.86 (m, 2H), 5.11-5.03 (m,
4H), 4.84 (br s, 2H), 3.77 (s, 3H), 3.19 (qd, J = 15.1, 6.8 Hz, 4H).
13C NMR (150 MHz, CDCl3): δ (ppm) 156.4, 152.3, 136.8, 136.4,
131.9, 116.3, 113.5, 94.2, 55.5, 35.9. HRMS (ESI): calculated for
C15H18Cl3N2O ([M+H]+): 347.0479; found 347.0491.
N-(3-allylbiphenyl-4-yl)-2,2,2-trichloroacetimidamide (3g). The
titled compound 3g was prepared by following the GP A. The prod-
uct 3g was isolated as white sticky solid (38 mg, 54%) and in a
second fraction product 4g was also isolated as sticky solid (16 mg,
20%). IR (neat): 3473, 3452, 2923, 1685, 1658, 1586, 1478, 917
cm-1. 1H NMR (600 MHz, CDCl3) δ 7.59 (d, J = 7.3 Hz, 2H), 7.50
(s, 1H), 7.47 (dd, J = 8.1, 1.8 Hz, 1H), 7.43 (t, J = 7.7 Hz, 2H), 7.33
(t, J = 7.4 Hz, 1H), 6.91 (d, J = 8.0 Hz, 1H), 5.99-5.92 (m, 1H),
5.12 (d, J = 17.0 Hz, 1H), 5.05 (d, J = 9.9 Hz, 1H), 4.98 (br s, 2H),
3.35 (d, J = 6.7 Hz, 2H). 13C NMR (150 MHz, CDCl3): δ (ppm)
152.3, 144.8, 140.9, 137.5, 136.9, 132.3, 129.1, 128.9, 127.2,
127.0, 126.3, 120.3, 116.1, 94.4, 36.1. HRMS (ESI): Calculated for
C17H16Cl3N2 ([M+H]+): 353.0374; found 353.0374.
N-(2-allyl-4-chlorophenyl)-2,2,2-trichloroacetimidamide (3d).
The titled compound 3d was prepared by following the GP A. The
product 3d was isolated as sticky white solid (35 mg, 56%) and in
a second fraction product 4d was also isolated as white sticky solid
(11 mg, 15%). IR (neat): 3488, 3385, 2924, 1666, 1587, 1477,
1337, 920 cm-1. 1H NMR (600 MHz, CDCl3): δ (ppm) 7.24 (s, 1H),
7.19 (dd, J = 8.3, 2.2 Hz, 1H), 6.77 (d, J = 8.3 Hz, 1H), 5.90-5.83
(m, 1H), 5.10-5.01 (m, 2H), 4.94 (br s, 2H), 3.25 (d, J = 6.7 Hz,
2H). 13C NMR (150 MHz, CDCl3): δ (ppm) 152.6, 144.0, 136.1,
133.9, 130.3, 129.7, 127.6, 121.2, 116.7, 94.2, 35.7. HRMS (ESI):
calculated for C11H11Cl4N2 ([M+H]+): 310.9671; found 310.9670.
2,2,2-trichloro-N-(3,5-diallylbiphenyl-4-yl)acetimidamide (4g).
The titled compound 4g was prepared by following the GP C and
isolated as white solid (55 mg, 70%). IR (neat): 3483, 3376, 3072,
2922, 1667, 1581, 1457, 915 cm-1. 1H NMR (600 MHz, CDCl3) δ
7.58 (ppm) (d, J = 7.6 Hz, 2H), 7.42 (t, J = 7.7 Hz, 2H), 7.36 (s,
2H), 7.32 (t, J = 7.3 Hz, 1H), 6.00-5.93 (m, 2H), 5.13 (d, J = 17.0
Hz, 2H), 5.07 (d, J = 10.0 Hz, 2H), 4.89 (br s, 2H), 3.29 (qd, J =
15.2, 6.8 Hz, 4H). 13C NMR (150 MHz, CDCl3): δ (ppm) 151.7,
142.6, 141.0, 137.2, 136.9, 131.1, 128.9, 127.1, 127.0, 126.9,
2,2,2-trichloro-N-(2,6-diallyl-4-chlorophenyl)acetimidamide
(4d). The titled compound 4d was prepared by following the GP C
and isolated as white sticky solid (51 mg, 72%). IR (neat): 3469,
3370, 2924, 2852, 1607, 1477, 1439, 738 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 7.09 (s, 2H), 5.90-5.83 (m, 2H), 5.12-5.04 (m,
4H), 4.86 (br s, 2H), 3.23-3.12 (m, 4H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.0, 141.7, 136.0, 132.6, 129.5, 128.0, 116.9,
93.9, 35.5. HRMS (ESI): calculated for C14H15Cl4N2 ([M+H]+):
350.9984; found 350.9992.
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116.3, 94.1, 35.9. HRMS (ESI): Calculated for C20H20Cl3N2
1H), 7.07 (d, J = 6.5 Hz, 1H), 5.89-5.83 (m, 1H), 5.14-5.11(m, 2H),
([M+H]+): 393.0687; found 393.0689.
4.95 (br s, 2H), 3.29 (d, J = 6.8 Hz, 2H). 13C NMR(150 MHz,
CDCl3): δ (ppm) 156.54 (d, J = 250.8 Hz), 153.4, 141.2, 138.92 (d,
J = 7.5 Hz), 134.95, 122.47 (q, J = 272.1 Hz), 118.60 (d, J = 21.6
Hz), 118.32 (q, J = 3.3 Hz), 117.7, 117.18 (qd, J = 33.3, 13.8 Hz),
94.0, 35.6. 19F NMR (376 MHz, CDCl3) δ (ppm) -61.03 (d, J = 12.7
Hz, 3F), -120.82 (q, J = 12.7 Hz, 1F). HRMS (ESI): calculated for
C12H10Cl3F4N2 ([M+H]+): 362.9840; found 362.9842.
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N-(2-allyl-5-methylphenyl)-2,2,2-trichloroacetimidamide (3h).
The titled compound 3h was prepared by following the GP A and
isolated as white sticky solid (34.5 mg, 59%). IR (neat): 3469,
3362, 2922, 1660, 1583, 837, 784 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 7.12 (d, J = 7.7 Hz, 1H), 6.88 (d, J = 7.7 Hz, 1H),
6.64 (s, 1H), 5.92-5.85 (m, 1H), 5.05 (d, J = 18.3 Hz, 1H), 4.99 (d,
J = 10.0 Hz, 1H), 4.91 (br s, 2H), 3.23 (d, J = 6.8 Hz, 2H), 2.30 (s,
3H). 13C NMR (150 MHz, CDCl3): δ (ppm) 152.1, 146.3, 137.4,
137.3, 130.2, 128.6, 125.3, 120.3, 115.6, 94.5, 35.5, 21.1. HRMS
(ESI): calculated for C12H14Cl3N2 ([M+H]+): 291.0217; found
291.0223.
N-(2-allyl-6-methylphenyl)-2,2,2-trichloroacetimidamide (3m).
The titled compound 3m was prepared by following the GP A and
isolated as gummy white solid (45.5 mg, 78%). IR (neat): 3483,
3375, 2917, 1665, 1584, 1460, 1338, 860 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 7.07 (d, J = 7.5 Hz, 2H), 6.98 (t, J = 7.5 Hz, 1H),
5.94-5.87 (m, 1H), 5.07 (d, J = 17.0 Hz, 1H), 5.01 (d, J = 10.0 Hz,
1H), 4.83 (br s, 2H), 3.23 (d, J = 6.8 Hz, 2H), 2.12 (s, 3H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 151.3, 143.6, 137.1, 130.7,
129.1, 128.2, 127.7, 124.2, 115.9, 94.1, 36.0, 17.3. HRMS (ESI):
calculated for C12H14Cl3N2 ([M+H]+): 291.0217; found 291.0219.
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N-(2-allyl-5-methoxyphenyl)-2,2,2-trichloroacetimidamide (3i).
The titled compound 3i was prepared by following the GP A and
isolated as white sticky solid (47 mg, 77%). IR (neat): 3403, 3312,
1
2928, 2834, 1657, 1600, 1581, 791 cm-1. H NMR (600 MHz,
CDCl3): δ (ppm) 7.14 (d, J = 8.4 Hz, 1H), 6.63 (dd, J = 8.4, 2.5 Hz,
1H), 6.39 (d, J = 2.5 Hz, 1H), 5.92-5.85 (m, 1H), 5.06-4.97 (m,
2H), 4.95 (br s, 2H), 3.78 (s, 3H), 3.20 (d, J = 6.6 Hz, 2H). 13C
NMR (150 MHz, CDCl3): δ (ppm) 159.2, 152.3, 146.3, 137.4,
131.3, 123.7, 115.5, 110.2, 105.4, 94.4, 55.6, 35.1. HRMS (ESI):
calculated for C12H14Cl3N2O ([M+H]+): 307.0166; found
307.0168.
N-(6-allyl-2,3-dimethylphenyl)-2,2,2-trichloroacetimidamide
(3n). The titled compound 3n was prepared by following the GP A
and isolated as gummy white solid (47 mg, 77%). IR (neat): 3463,
1
3359, 2923, 2854, 1681, 1661, 1582 cm-1. H NMR (600 MHz,
CDCl3): δ (ppm) 6.97 (d, J = 7.7 Hz, 1H), 6.88 (d, J = 7.7 Hz, 1H),
5.93-5.87 (m, 1H), 5.06 (d, J = 17.0 Hz, 1H), 5.00 (d, J = 9.9 Hz,
1H), 4.80 (br s, 2H), 3.19 (d, J = 6.7 Hz, 2H), 2.26 (s, 3H), 2.02 (s,
3H). 13C NMR (150 MHz, CDCl3): δ (ppm) 151.2, 143.5, 137.4,
136.0, 128.2, 127.1, 126.5, 125.7, 115.7, 94.2, 36.0, 20.3, 13.4.
HRMS (ESI): calculated for C13H16Cl3N2 ([M+H]+): 305.0374;
found 305.0369.
2,2,2-trichloro-N-(2,6-diallyl-3-methoxyphenyl)acetimidamide
(4i). The titled compound 4i was prepared by following the GP B
and isolated as white sticky solid (10.5 mg, 15%). The major prod-
uct 3i of this reaction was isolated in a second fraction (43 mg,
70%). IR (neat): 3435, 3312, 2936, 2834, 1642, 1581, 1477, 1267
1
cm-1. H NMR (600 MHz, CDCl3): δ (ppm) 7.05 (d, J = 8.4 Hz,
N-(2-allyl-6-fluorophenyl)-2,2,2-trichloroacetimidamide (3o).
The titled compound 3o was prepared by following the GP A and
isolated as white sticky solid (42.5 mg, 72%). IR (neat): 3477,
2962, 1656, 1588, 1460, 781, 761 cm-1. 1H NMR (400 MHz,
CDCl3): δ (ppm) 7.06-6.96 (m, 3H), 5.93-5.83 (m, 1H), 5.09-5.01
(m, 4H), 3.31 (d, J = 6.7 Hz, 2H). 13C NMR (100 MHz, CDCl3): δ
(ppm) 153.1, 152.81 (d, J = 244 Hz ), 136.5, 135.09 (d, J= 2 Hz),
132.61 (d, J = 13 Hz), 125.50 (d, J = 3.1 Hz), 124.99 (d, J = 8 Hz),
116.2, 114.28 (d, J = 20 Hz), 94.07, 35.86 (d, J = 2 Hz). 19F NMR
(376 MHz, CDCl3): δ (ppm) -125.5 (s, 1F). HRMS (ESI): calcu-
lated for C11H11Cl3FN2 ([M+H]+): 294.9966; found 294.9968.
1H), 6.62 (d, J = 8.4 Hz, 1H), 5.90-5.85 (m, 2H), 5.11-4.95 (m,
3H), 4.93-4.86 (m, 1H), 4.81 (br s, 2H), 3.82 (s, 3H), 3.29-3.21 (m,
2H), 3.19-3.09 (m, 2H). 13C NMR (150 MHz, CDCl3): δ (ppm)
157.0, 151.5, 144.3, 137.4, 136.8, 128.3, 122.8, 119.0, 115.7,
114.9, 106.5, 94.2, 55.8, 35.1, 29.9. HRMS (ESI): calculated for
C15H18Cl3N2O ([M+H]+): 347.0479; found 347.0483.
2,2,2-trichloro-N-(2,6-diallyl-3,4-imethoxyphenyl)
acetimIdamide (4j). The titled compound 4j was prepared by fol-
lowing the GP C and isolated as white sticky solid (32 mg, 42%).
IR (neat): 3453, 3357, 2925, 2853, 1659, 1463, 1231, 821 cm-1. 1H
NMR (600 MHz, CDCl3): δ (ppm) 6.68 (s, 1H), 5.93-5.84 (m, 2H),
5.09 (d, J = 18.5 Hz, 1H), 5.05 (s, 1H), 5.03 (d, J = 7.4 Hz, 1H),
4.93 (d, J = 10.0 Hz, 1H), 4.84 (br s, 2H), 3.83 (s, 3H), 3.80 (s, 3H),
3.31-3.22 (m, 2H), 3.20-3.10 (m, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.2, 149.4, 146.5, 137.0, 136.9, 136.8, 125.5,
125.4, 116.2, 115.3, 112.1, 94.3, 60.9, 56.0, 35.5, 30.5. HRMS
(ESI): calculated for C16H20Cl3N2O2 ([M+H]+): 377.0585; found
377.0584.
2,2,2-trichloro-N-(2,6-diallyl-4-ethylphenyl)acetimidamide
(4p). The titled compound 4p was prepared by following the GP C
and isolated as gummy white solid (29 mg, 42%). IR (neat): 3469,
3361, 2964, 2929, 1659, 1582, 1463, 910 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 6.93 (s, 2H), 5.95-5.88 (m, 2H), 5.08 (d, J = 17.0
Hz, 2H), 5.02 (d, J = 10.0 Hz, 2H), 4.83 (br s, 2H), 3.19 (qd, J =
15.1, 6.8 Hz, 4H), 2.59 (q, J = 7.6 Hz, 2H), 1.22 (t, J = 7.6 Hz, 3H).
13C NMR (150 MHz, CDCl3): δ (ppm) 151.6, 140.8, 140.1, 137.2,
130.4, 127.6, 115.9, 94.2, 35.9, 28.5, 15.8. HRMS (ESI): calculated
for C16H20Cl3N2 ([M+H]+): 345.0687; found 345.0686.
N-(2-allyl-5-chlorophenyl)-2,2,2-trichloroacetimidamide (3k).
The titled compound 3k was prepared by following the GP A and
isolated as gummy white solid (45 mg, 72%). IR (neat): 3371, 2926,
2857, 1665, 1586, 1478, 834, 789 cm-1. 1H NMR (600 MHz,
CDCl3): δ (ppm) 7.18 (d, J = 8.2 Hz, 1H), 7.05 (dd, J = 8.2, 2.1 Hz,
1H), 6.85 (d, J = 2.1 Hz, 1H), 5.90-5.83 (m, 1H), 5.07-5.02 (m,
2H), 4.98 (br s, 2H), 3.24 (d, J = 6.7 Hz, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 152.6, 146.6, 136.5, 132.8, 131.6, 130.5, 124.5,
119.9, 116.3, 94.2, 35.3. HRMS (ESI): calculated for C11H11Cl4N2
([M+H]+): 310.9671; found 310.9692.
2,2,2-trichloro-N-(2,6-diallyl-4-bromophenyl)acetimidamide
(4q). The titled compound 4q was prepared by following the GP C
and isolated as white sticky solid (61 mg, 77%). IR (neat): 3487,
3384, 2922, 1650, 1584, 1448, 914, 832 cm-1. 1H NMR (400 MHz,
CDCl3): δ (ppm) 7.24 (s, 2H), 5.92-5.82 (m, 2H), 5.12-5.06 (m,
4H), 4.87 (br s, 2H), 3.17 (qd, J = 15.3, 6.7 Hz, 4H). 13C NMR (100
MHz, CDCl3): δ (ppm) 151.9, 142.3, 136.0, 133.0, 130.9, 117.4,
117.0, 93.9, 35.4. HRMS (ESI): calculated for C14H15BrCl3N2
([M+H]+): 394.9479; found 394.9482.
N-(2-allyl-4-fluoro-5-(trifluoromethyl)phenyl)-2,2,2-trichloro
acetimidamide (3l). The titled compound 3l was prepared by fol-
lowing the GP A and isolated as gummy white solid (38.5 mg,
53%). IR (neat): 3466, 3422, 3296, 2924, 2852, 1636, 1495, 1413
(E)-N-(2-(but-2-en-1-yl)phenyl)-2,2,2-trichloroacetimidamide
(3r).10a,14 The titled compound 3r was prepared by following the
GP A and isolated as white sticky solid (40 mg, 69%, E/ Z 1:4). IR
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1
cm-1. H NMR (600 MHz, CDCl3): δ (ppm) 7.11 (d, J = 10.9 Hz,
(neat): 3484, 3380, 2923, 2854, 1655, 1587, 1334, 791 cm-1. H
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The Journal of Organic Chemistry
NMR (400 MHz, CDCl3): δ (ppm) 7.26-7.19 (m, 2H), 7.07 (t, J =
N-(3,5-diallyl-4-(2,2,2-trichloroacetimidamido)phenyl)acetam-
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6
7
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7.3 Hz, 1H), 6.81 (d, J = 7.6 Hz, 1H), 5.57-5.47 (m, 2H), 4.92 (s,
2H), 3.22 (s, 2H), 1.66 (d, J = 2.1 Hz, 3H). 13C NMR (100 MHz,
CDCl3): δ (ppm) 152.1, 145.4, 132.7, 130.3, 129.5, 127.4, 126.5,
124.5, 119.8, 94.5, 34.7, 18.0. HRMS (ESI): calculated for
C12H14Cl3N2 ([M+H]+): 291.0217; found 291.0224.
ide (10). The titled compound 10 was synthesized according to the
GP C and isolated as sticky solid (61.5 mg, 81%). mp 219-221 oC.
IR (KBr): 3446, 3350, 1656, 1606, 1551, 1462 cm-1. 1H NMR (600
MHz, CDCl3): δ (ppm) 7.22 (s, 2H), 5.91-5.85 (m, 2H), 5.10-5.03
(m, 4H), 4.90 (s, 2H), 3.23-3.14 (m, 4H), 2.14 (s, 3H). 13C NMR
(150 MHz, CDCl3): δ (ppm) 168.5, 152.1, 136.5, 134.1, 131.6,
120.5, 116.5, 94.1, 35.8, 24.6. HRMS (ESI): calculated for
C16H19Cl3N3O ([M+H]+): 374.0588; found 374.0610.
2,2,2-trichloro-N-(2-(3-methylbut-2-en-1-)phenyl)
acetimidamide (3s). The titled compound 3s was prepared by fol-
lowing the GP A and isolated as white sticky solid (42 mg, com-
bined yield 68%) as 9:1 mixture of 3s and 4s. IR (neat): 3430, 2925,
(E)-ethyl 3-(2-(2,2,2-trichloroacetimidamido)phenyl)acrylate
(11a). The titled compound 11a was synthesized according to the
GP D and isolated as sticky solid (28.2 mg, 42%). IR (KBr): 2928,
9
1
2853, 1649, 1593, 817, 788 cm-1. H NMR (600 MHz, CDCl3) δ
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7.24 (d, J = 7.6 Hz, 1H), 7.19 (t, J = 7.4 Hz, 1H), 7.08-7.05 (m,
1H), 6.80 (d, J = 7.7 Hz, 1H), 5.24 (t, J = 7.2 Hz, 1H), 4.92 (s, 2H),
3.22 (d, J = 7.0 Hz, 2H), 1.71 (s, 3H), 1.69 (s, 3H). 13C NMR (150
MHz, CDCl3): δ (ppm) 152.1, 145.4, 133.3, 132.7, 130.1, 127.2,
124.5, 122.7, 119.7, 94.5, 30.0, 25.9, 18.0. HRMS (ESI): calculated
for C13H16Cl3N2 ([M + H]+): 305.0374, found 305.0388.
1
2856, 1719, 1687, 1655 cm-1. H NMR (400 MHz, DMSO-d6): δ
(ppm) 7.78 (d, J = 7.8 Hz, 1H), 7.66 (d, J = 16.1 Hz, 1H), 7.38 (t, J
= 7.6 Hz, 1H), 7.10 (t, J = 7.6 Hz, 1H), 6.89 (s, 2H), 6.81 (d, J =
7.9 Hz, 1H), 6.53 (d, J = 16.1 Hz, 1H), 4.13 (q, J = 7.0 Hz, 2H),
1.21 (t, J = 7.1 Hz, 3H). 13C NMR (100 MHz, DMSO-d6): δ (ppm)
166.4, 153.1, 147.9, 140.6, 131.6, 127.8, 125.1, 123.6, 121.2,
117.7, 95.1, 59.9, 14.2. HRMS (ESI): calculated for C13H14Cl3N2O2
([M+H]+): 335.0115; found 335.0114.
2-(2,6-Diallylphenyl)pyridine (6).24 The titled compound 6 was
prepared by following the GP A and isolated as a colorless liquid
(28 mg, 64%) as 1.66:1 mixture of 6 and its diallylated product. 1H
NMR (600 MHz, CDCl3): δ (ppm) 8.72-8.67 (m, 1H), 7.73-7.10
(m, 1H), 7.40 (dd, J = 7.5, 4.3 Hz, 2H), 7.37-7.33 (m, 1H), 7.33-
7.28 (m, 3H), 5.92-5.85 (m, 1H), 4.96 (d, J = 10.0 Hz, 1H), 4.91 (d,
J = 9.1 Hz, 1H), 3.50 (d, J= 6.4 Hz, 2H). 13C NMR (150 MHz,
CDCl3): δ (ppm) 160.0, 149.3, 140.6, 137.8, 137.7, 136.3, 130.2,
130.0, 128.4, 126.4, 124.3, 121.9, 115.6, 37.5.
(E)-tert-butyl 3-(2-(2,2,2-trichloroacetimidamido)phenyl)acry-
late (11b). The titled compound 11b was synthesized according to
the GP D and isolated as sticky solid (36.4 mg, 50%). IR (KBr):
1
3448, 2978, 2928, 1688, 1596, 1476 cm-1. H NMR (400 MHz,
DMSO-d6): δ (ppm) 7.76 (d, J = 7.9 Hz, 1H), 7.58 (d, J = 16.1 Hz,
1H), 7.37 (t, J = 7.6 Hz, 1H), 7.09 (t, J = 7.5 Hz, 1H), 6.87 (s, 2H),
6.80 (d, J = 7.9 Hz, 1H), 6.40 (d, J = 16.1 Hz, 1H), 1.44 (s, 9H).
13C NMR (100 MHz, DMSO-d6): δ (ppm) 165.7, 153.0, 147.8,
139.6, 131.4, 127.5, 125.2, 123.6, 121.1, 119.4, 95.1, 79.6, 27.9.
HRMS (ESI): calculated for C15H17Cl3N2NaO2 ([M+Na]+):
385.0248; found 384.8621.
N-(p-tolyl)benzimidamide (7). The title compound 7 was synthe-
sized according to the literature procedure.25 A mixture of AlCl3
(1.47g, 11.0 mmol, 1.1 equiv), aniline (1.02g, 11.0 mmol, 1.1
equiv) and benzonitrile (1.03g, 10.0 mmol, 1.0 equiv) was stirred
o
at 130 C under an inert atmosphere in a sealed tube for about an
hour. The hot mixture was poured into a mixture of concentrated
NaOH (40 mL) containing ice-water (100 mL) and stirred for about
15 minutes. Then the mixture was extracted with EtOAc (25 mL
×3). The combined organic layers were washed with brine (30 mL
×3), dried over anhydrous Na2SO4, and evaporated under vacuum.
The residue was purified by silica gel column (30% ethyl acetate in
hexane) and isolated as white solid (1.5 g, 74%). 1H NMR (600
MHz, CDCl3): δ (ppm) 7.85 (s, 2H), 7.48-7.42 (m, 3H), 7.16 (d, J
= 7.5 Hz, 2H), 6.89 (d, J = 7.8 Hz, 2H), 4.83 (s, 2H), 2.33 (s, 3H).
13C NMR (150 MHz, CDCl3): δ (ppm) 155.1, 147.0, 136.0, 132.5,
130.6, 130.2, 128.6, 126.9, 121.6, 21.0.
(E)-ethyl
3-(3-methyl-2-(2,2,2-trichloroacetimidamido)phe-
nyl)acrylate (11c). The titled compound 11c was synthesized ac-
cording to the GP D and isolated as sticky solid (39.2 mg, 56%). IR
1
(KBr): 2926, 2954, 1688, 1626, 1460 cm-1. H NMR (600 MHz,
DMSO-d6): δ (ppm) 7.63-7.60 (m, 2H), 7.26 (d, J = 7.3 Hz, 1H),
7.00 (t, J = 7.6 Hz, 1H), 6.80 (s, 2H), 6.47 (d, J = 16.1 Hz, 1H),
4.17-4.10 (m, 2H), 2.03 (s, 3H), 1.21 (t, J = 7.1 Hz, 3H). 13C NMR
(150 MHz, DMSO-d6): δ (ppm) 166.4, 152.2, 146.4, 141.1, 132.6,
128.7, 125.1, 124.2, 123.2, 117.3, 94.8, 59.8, 17.1, 14.3. HRMS
(ESI): calculated for C14H16Cl3N2O2 ([M+H]+): 349.0272; found
349.0275.
N-(2-allyl-4-methylphenyl)benzimidamide (8). The titled com-
pound 8 was prepared by following the GP C and isolated as yellow
solid (31 mg, 62%). mp 210-212 oC. IR (KBr): 3420, 3058, 2921,
1638, 1572, 1488 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm). 7.89
(d, J = 6.4 Hz, 2H), 7.50-7.42 (m, 3H), 7.06 (s, 1H), 7.02 (d, J =
7.7 Hz, 1H), 6.80 (d, J = 7.8 Hz, 1H), 6.00-5.90 (m, 1H), 5.07-4.98
(m, 2H), 4.74 (s, 2H), 3.32 (d, J = 6.7 Hz, 2H), 2.32 (s, 3H). 13C
NMR (100 MHz, CDCl3): δ (ppm). 154.3, 145.1, 137.7, 136.0,
132.7, 131.8, 130.7, 130.6, 128.7, 128.0, 126.9, 121.2, 115.3, 36.2,
21.0. HRMS (ESI): calculated for C17H19N2 ([M+H]+): 251.1543;
found 251.1551.
(E)-ethyl
3-(4-methyl-2-(2,2,2-trichloroacetimidamido)phe-
nyl)acrylate (11d). The titled compound 11d was synthesized ac-
cording to the GP D and isolated as sticky solid (28 mg, 40%). IR
1
(KBr): 3440, 2926, 2854, 1686, 1604, 1486 cm-1. H NMR (600
MHz, DMSO-d6): δ (ppm) 7.67 (d, J = 8.0 Hz, 1H), 7.63 (d, J =
16.1 Hz, 1H), 6.92 (d, J = 8.0 Hz, 1H), 6.86 (s, 2H), 6.63 (s, 1H),
6.47 (d, J = 16.1 Hz, 1H), 4.12 (q, J = 7.1 Hz, 2H), 2.30 (s, 3H),
1.21 (t, J = 7.1 Hz, 3H). 13C NMR (150 MHz, DMSO-d6): δ (ppm)
166.5, 152.9, 147.8, 141.6, 140.6, 127.8, 124.5, 122.4, 121.5,
116.5, 95.1, 59.7, 21.1, 14.2. HRMS (ESI): calculated for
C14H16Cl3N2O2 ([M+H]+): 349.0272; found 349.0278.
N-(4-(2,2,2-trichloroacetimidamido)phenyl)acetamide (9). The
ASSOCIATED CONTENT
Supporting Information
titled compound
9
was synthesized from N-acetyl-p-
phenylenediamine using GP I and isolated as white solid (1.77 g,
o
60%). mp 160-162 C. IR(KBr): 3445, 3295, 3118, 1654, 1604,
1541 cm-1. 1H NMR (400 MHz, CDCl3): δ (ppm) 7.63 (s, 1H), 7.45
(d, J = 8.6 Hz, 2H), 6.86 (d, J = 8.6 Hz, 2H), 5.09 (s, 2H), 2.14 (s,
3H). 13C NMR (100 MHz, CDCl3): δ (ppm) 169.0, 134.29, 134.28,
122.1, 121.3, 94.5, 24.4. HRMS (ESI): calculated for
C10H11Cl3N3O ([M+H]+): 293.9962; found 293.9971.
The Supporting Information is available free of charge on the ACS
Publications website.
Experimental details, crystallographic data of 11a, and NMR spec-
tra (PDF).
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(8) (a) Tran, D. N.; Cramer, N. Angew. Chem. Int. Ed. 2010, 49,
8181. (b) Tsai, A. S.; Brasse, M.; Bergman, R. G.; Ellman, J. A. Org.
Lett. 2011, 13, 540.
AUTHOR INFORMATION
Corresponding Author
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5
(9) Zeng, R.; Fu, C.; Ma, S. J. Am. Chem. Soc. 2012, 134, 9597.
(10) (a) Wang, H.; Schrçder, N.; Glorius, F. Angew. Chem. Int. Ed.
2013, 52, 5386. (b) Shi, Z.; Boultadakis-Arapinis, M.; Glorius, F.
Chem. Commun. 2013, 49, 6489.
*E-mail: msm@chem.iitkgp.ernet.in
Notes
The authors declare no competing financial interest.
(11) (a) Zhang, S.-S.; Wu, J.-Q.; Liu, X.; Wang, H. ACS Catal. 2015,
5, 210. (b) Wu, J.-Q.; Qiu, Z.-P.; Zhang, S.-S.; Liu, J.-G.; Lao, Y.-X.;
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Feng, C.; Feng, D.; Loh, T.-P. Chem. Commun. 2015, 51, 342. (c) Li,
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T.; Yang, S.; Chen, S.; Li, X. Org. Biomol. Chem. 2014, 12, 4290.
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2013, 15, 4576. (b) Kim, M.; Park, J.; Sharma, S.; Han, S.; Han, S. H.;
Kwak, J. H.; Jung, Y. H.; Kim, I. S. Org. Biomol. Chem. 2013, 11,
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ACKNOWLEDGMENT
M.S.M. gratefully acknowledges SERB, Department of Science
and Technology, India (Sanction No. EMR/2015/000994) for fund-
ing. SSB thanks CSIR India and SD thanks IIT Kharagpur for fel-
lowship. We thank Dr. M. C. Das for helpful discussion.
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