Ruthenium(II)-catalyzed protocol for preparation of diverse α,β- and β,β-Dihaloenones from diazodicarbonyls

Article abstract of DOI:10.1002/adsc.201400348

Efficient one-step syntheses of α,β- and β,β-dihaloenones were achieved by ruthenium(II)- catalyzed reactions between cyclic or acyclic diazodicarbonyl compounds and oxalyl chloride or oxalyl bromide in moderate to good yields. This methodology offers sev

Full text of DOI:10.1002/adsc.201400348

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DOI: 10.1002/adsc.201400348
Ruthenium(II)-Catalyzed Protocol for Preparation of Diverse
a,b- and b,b-Dihaloenones from Diazodicarbonyls
Krishna Bahadur Somai Magara and Yong Rok Leea,*
a
School of Chemical Engineering, Yeungnam University, Gyeongsan 712-749, Republic of Korea
Fax : (+82)-53-810-4631; phone: (+82)-53-810-2529; e-mail: yrlee@yu.ac.kr
Received: April 7, 2014; Revised: June 23, 2014; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400348.
Abstract: Efficient one-step syntheses of a,b- and non-toxic catalyst. The synthesized compounds were
b,b-dihaloenones were achieved by ruthenium(II)- further transformed into highly functionalized novel
catalyzed reactions between cyclic or acyclic diazodi- molecules bearing aromatic rings on the enone
carbonyl compounds and oxalyl chloride or oxalyl moiety using the Suzuki reaction.
bromide in moderate to good yields. This methodolo-
gy offers several significant advantages, which in- Keywords: diazodicarbonyl compounds; a,b-dihalo-
clude ease of handling, mild reaction conditions,
ACHTUNGTRENeNGNU nones; b,b-dihaloenones; ruthenium(II)-catalyzed
one-step reaction, and the use of an effective and reaction
Introduction
chlorine and phosgene, the product mixtures pro-
duced, long reaction times, and harsh reaction condi-
Molecules bearing a- and b-haloenones are found in tions. Thus, there is demand for general and facile
nature and have been shown to possess potent biolog- synthetic methods that efficiently provide a variety of
ical activities.[1] a-Haloenones and b-haloenones are a,b- or b,b-dihaloenones under mild catalytic condi-
important synthetic intermediates because various tions.
substituents can be installed at their a- and b-posi-
The decomposition of diazocarbonyl compounds
tions to synthesize biologically active natural prod- has been widely used in organic synthesis,[14] and tran-
ucts.[2,3] Because of their importance and usefulness, sition metal-catalyzed reactions between diazocarbon-
various synthetic methods have been developed for a- yls and substrates have become important for the syn-
haloenones and b-haloenones.[4,5] Synthetic procedures thesis of a wide variety of heterocycles.[15] We have in-
for a-haloenones generally utilize halogenation–dehy- vestigated metal(II)-catalyzed or thermal reactions
drohalogenation,[6] an addition–elimination,[7] or halo- between diazo compounds and different sub-
hydrin dehydration.[8] In addition, gold-catalyzed reac- strates.[16–18] In particular, we developed a method for
tions of propargylic acetates to give a-haloenones preparing a variety of a-haloenones using rhodiu-
have been described.[9] Recently, a number of synthet- m(II)-catalyzed reactions between cyclic diazodicar-
ic approaches have been reported for b-haloenones, bonyl compounds and acid chlorides[19] or benzyl hal-
such as the Brønsted acid-promoted cyclization of 1- ides.[20] In the related work, an a-halogenation reac-
siloxy-1,5-diynes[10] and halogen-induced 1,2-silyl mi- tion between acyclic diazo compounds and dihalome-
gration reaction.[11] Importantly, the 3-step synthetic thanes has been reported by another group,[21] and the
route to a,b-dihaloenones from cyclohexane-1,3-dione formation of a-haloenones from iodonium ylides has
using very toxic chlorine and phosgene has been re- been accomplished by Moriartyꢀs group[22] and our
ported.[12] On the other hand, for the synthesis of b,b- own.[23] Recently, a hypervalent iodine reagent-based
dihaloenones, reactions between alkynols, containing a,a-dihalogenation of acyclic diazo compounds has
terminal bromine and iodine, and N-halosuccinimides been reported by Murphyꢀs group (Scheme 1).[24]
or hydroxy(tosyloxy)iodobenzene (HITB) have been
Our interest in developing a mild and efficient
described.[13] Although a number of methods have methodology to synthesize a variety of a,b- and b,b-
been discussed for the synthesis of a,b-dichloroenones dihaloenones prompted us to search for more conven-
and b,b-bromoiodoenones, these approaches have ient and safer catalysts. Previously, we used tris(tri-
a number of shortcomings, such as the use of toxic phenylphosphine)ruthenium(II) dichloride as a mild
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Krishna Bahadur Somai Magar and Yong Rok Lee
cyclic diazodicarbonyls or acyclic diazodicarbonyls
and oxalyl halides (Scheme 2).
Results and Discussion
Our efforts commenced with the preparation of cyclic
diazodicarbonyl compounds 1a–1s (65–92%) and acy-
clic diazodicarbonyl compounds 1t–1w (85–91%)
from the corresponding 1,3-dicarbonyls using a previ-
ously reported protocol (Table 1).[27]
In order to prepare a,b-dihaloenones, we first ex-
amined the reaction between the cyclic diazodicar-
bonyl compound 1a with chlorinating reagents, which
Scheme 1. Recently reported a,a-chlorination and a,a-fluo-
rination reactions starting from diazo compounds.
catalyst to synthesize multi-substituted dihydrofurans serve as solvent and reactant, in the presence of 0–
from diazodicarbonyls.[25] In our opinion, Ru(II)-phos- 5 mol% of RuCl
CTHUNGTRENNUNG
phine complexes provide a promising basis for the in Table 2. Treatment of 1a (1.0 mmol) with oxalyl
syntheses of a,b- or b,b-dihaloenones, because they chloride (1.5 mL) without a catalyst at room tempera-
are readily available, generally non-toxic, and have ture for 24 h did not provide any products, whereas
high catalytic activities.[26]
reaction at 508C for 24 h provided the product 2a in
To the best of our knowledge, no one-pot synthesis 27% yield. In the catalyst-free conditions, formation
of a,b- and b,b-dihaloenones starting from diazo com- of 2a could be explained due to the generation of car-
pounds has been published to date. Here, we first bene via thermal decomposition of diazo compound
report the efficient, facile one-pot synthesis of a,b-di- 1a. Using RuCl2ACTHNUTRGEN(UNG PPh3)3 as a catalyst, we attempted
haloenones [Eq. (1)] and b,b-dihaloenones [Eq. (2)] further reactions by changing the chlorinating re-
using ruthenium(II)-catalyzed reactions between agents, for example, diethyl chlorophosphate, thionyl
chloride, sulfuryl chloride, phosphorus oxychloride, or
phosphorus trichloride (entries 3–12). To our delight,
with oxalyl chloride in the presence of 2 mol% of
RuCl2ACHTNUGTRNEUNG(PPh3)3 at 508C for 5 h, 2a was produced in the
best yield (88%) (entry 5). In addition, after reaction
with oxalyl chloride (1.5 mmol) in PhF at 508C for
12 h, 2a was isolated in 70% yield (entry 7). When the
other chlorinating reagents were used, the yield of 2a
decreased (entries 8–12). Support for the structural
assignment of 2a was obtained by spectroscopic analy-
sis. Compound 2a was identified by its IR enone car-
bonyl absorptions at 1693 cmÀ1 and two methylene
protons, which appeared as two singlets at d=2.69
Scheme 2.
Table 1. Cyclic diazodicarbonyl compounds 1a–1s and acyclic diazodicarbonyl compounds 1t–1w.
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Ruthenium(II)-Catalyzed Protocol for Preparation of Diverse a,b- and b,b-Dihaloenones
Table 2. Optimization of reaction conditions.[a]
Table 3. Formation of a variety of a,b-dichloroenones 2b–2r
and a,b-dibromoenones 3a–3j by RuCl2ACHTNUGTRNEG(UN PPh3)3-catalyzed re-
action of cyclic diazodicarbonyl compounds.[a–c]
[a]
Reaction conditions: 1a (1.0 mmol) and chlorinating re-
agent (1.5 mL) under N2.
Isolated yield.
Oxalyl chloride (1.5 mmol) in PhF (3.0 mL).
[b]
[c]
1
and 2.42 ppm, respectively, in its H NMR spectrum.
In its 13C NMR spectrum, one enone carbonyl carbon
was observed at d=189.2 ppm together with two sp2
carbons at d=151.4 and 135.3 ppm. Furthermore, the
structure determination was established by X-ray
crystallographic analysis of structurally related com-
pound 2g (see the Supporting Information).[28]
Having optimized the reaction conditions, we fur-
ther explored the generality of the reaction by using
different cyclic diazodicarbonyl compounds. The re-
sults obtained are presented in Table 3. Reaction be-
tween 2-diazocyclohexane 1,3-dione (1b) and oxalyl
[a]
Reaction conditions for a,b-dichloroenones 2b–2r: diazo-
dicarbonyls (1.0 mmol) and oxalyl chloride (1.5 mL) in
the presence of 2 mol% of RuCl2ACTHNUTRGNEUNG(PPh3)3 at 508C for 5 h.
Reaction conditions for a,b-dibromoenones 3a–3j: diazo-
[b]
dicarbonyls (1.0 mmol) and oxalyl bromide (1.5 mmol) in
chloride in the presence of 2 mol% of RuCl2ACTHNUTRGEN(UNG PPh3)3
the presence of 2 mol% of RuCl
at room temperature for 10 h.
Isolated yields.
2ACHTUNGTREN(UNGN PPh3)3 in PhF (3.0 mL)
at room temperature for 10 h gave product 2b in 82%
yield. Similarly, reactions of cyclic diazodicarbonyl
compounds 1c–1h bearing various substituents, such
as methyl, isopropyl, 2-furanyl, phenyl, and aryl
groups at the 5-position on the 2-diazocyclohexane-
1,3-dione ring provided the desired products 2c–2h in
64–92% yields. We also tried further reactions using
solvent. For example, treatment of 1d and 1f with
[c]
[d]
Reactions were carried out at room temperature for
10 h.
Oxalyl chloride (1.5 mmol) in PhF (3.0 mL) at 508C for
12 h.
[e]
oxalyl chloride (1.5 mmol) in PhF at 508C for 12 h af- (Table 3). Treatment of 1a with oxalyl bromide in the
forded 2d and 2f in 63 and 74% yields, respectively. presence of 2 mol% of RuCl2A(PPh3)3 in fluorobenzene
CTHUNGTRENNUNG
When 2-diazo-1H-phenalene-1,3(2H)-dione (1i) was at room temperature for 10 h provided 3a in 63%
used, 2i was produced in a yield of 67%. For the yield. Importantly, in this case, a solvent was needed.
diazoACHTUNGTRENNUNGdicarbonyls 1j–1l with 5- and 7-membered rings, In the absence of solvent, pure products were not
the desired products 2j–2l were isolated in 57, 78, and formed and intractable mixtures were produced. Re-
51% yields, respectively. Encouragingly, reactions be- actions between 2-diazo-1H-phenalene-1,3(2H)-dione
tween 3-diazoquinoline-2,4
oxalyl chloride afforded the desired products 2m–2r oxalyl bromide in fluorobenzene at room temperature
in 66–77% yield. for 10 h afforded the products 3b (52%) and 3c
ACHTUNGTNER(NUNG 1H,3H)-diones 1n-1s and (1i) or 2-diazo-1H-indene-1,3(2H)-dione (1k) and
Next, we explored these reactions with oxalyl bro- (40%). Similarly, reaction between 3-diazochromane-
mide to produce a number of a,b-dibromoenones 2,4-dione (1m) and oxalyl bromide in fluorobenzene
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gave the desired product 3d in 43% yield. In addition, 4e in 62–72% yield. The structure of 4a was con-
treatment of 3-diazoquinoline-2,4(1H,3H)-diones 1n– firmed by analyzing its spectral data and by compar-
1s provided the desired products 3e–3j in 62–74% ing them with those of a commercially available stan-
yield. dard.
A proposed mechanism for the formation of 2a is The formation of 4a can be explained as shown in
AHCTUNGTRENNUNG
described in Scheme 3. The diazodicarbonyl com- Scheme 4. The diazodicarbonyl 1b first gives a,b-di-
pound 1a initially gives a metal carbenoid 4 due to bromoenone 7, which then undergoes enolization fol-
the displacement of nitrogen by RuCl2ACTHNUTRGNE(UNG PPh3)3. Then lowed by HBr elimination to furnish the stable aro-
nucleophilic attack on the electrophilic carbenoid 4 matic 4a. As evidence for this mechanism, the forma-
by chlorine of oxalyl chloride yields intermediate 5, tion of intermediate 8 from 7 has been described by
which undergoes the intramolecular nucleophilic ad- the Hendersonꢀs group.[30]
dition of oxygen to the carbonyl group and subse-
Next, further reactions between acyclic diazodicar-
À
quent cleavage of the C Cl bond to give 6. As an evi- bonyl compounds and oxalyl halides were attempted
dence for intermediate 5, a chloronium ylide inter- (Table 4). For example, treatment of the acyclic diazo-
mediate was already reported by our[19,20b] and other
groups.[22,29] Intramolecular nucleophilic addition of
the chlorine atom to the enone in 6 gives final prod-
uct 2a through decarboxylation and decarbonylation.
On the other hand, reactions between cyclic diazo-
dicarbonyl compounds 1b, 1d, 1f, 1g, and 1h bearing
a mono substituent or without any substituent on the
5-position of the 2-diazocyclohexane-1,3-dione ring
and oxalyl bromide did not provide the desired a,b-
dibromoenones instead the aromatized products 4a–
4e were produced (Figure 1). For example, treatment
of 1b with oxalyl bromide in the presence of 2 mol% Scheme 4.
of RuCl2ACHTUNGTRENNUNG(PPh3)3 in fluorobenzene at room tempera-
ture for 10 h gave aromatic compound 4a in 68%
yield. Similarly, reactions between 1d, 1f, 1g or 1h and
oxalyl bromide provided the aromatic compounds 4b–
Table 4. Formation of a variety of b,b-dichloroenones 9a–9d
and b,b-dibromoenones 10a, 10b by RuCl2ACHTNUGTRENUNG(PPh3)3-catalyzed
reaction of acyclic diazodicarbonyl compounds.[a–c]
Scheme 3.
[a]
Reaction conditions: acyclic diazodicarbonyls (1.0 mmol)
and oxalyl chloride (1.5 mL) in the presence of 2 mol%
of RuCl2ACTHNUGTRNEUNG(PPh3)3 at room temperature for 10 h.
Reaction conditions: acyclic diazodicarbonyls (1.0 mmol)
and oxalyl bromide (1.5 mmol) in the presence of
[b]
[c]
2 mol% of RuCl
perature for 10 h.
Isolated yields.
2ACHTUGNRTEN(NUNG PPh3)3 in PhF (3.0 mL) at room tem-
Figure 1.
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Ruthenium(II)-Catalyzed Protocol for Preparation of Diverse a,b- and b,b-Dihaloenones
dicarbonyl 1t with oxalyl chloride in the presence of
2 mol% of RuCl2A(PPh3)3 at room temperature for
CTHUNGTRENNUNG
10 h unexpectedly gave the b,b-dichloroenone 9a in
83% yield through a Wolff rearrangement. Unlike
cyclic diazodicarbonyl compounds, it was reported
that acyclic diazodicarbonyl compounds can be readi-
ly converted to the corresponding ketenes through
Wolff rearrangement in the presence of metal cata-
lysts at room temperature.[31] Using the acyclic diazo-
dicarbonyls 1u–1w, products 9b–9d were isolated in
93, 74, and 53% yields, respectively. Similarly, reac-
tions between 1v or 1w and oxalyl bromide in the
presence of 2 mol% of RuCl2ACHTNUGTRNEUNG(PPh3)3 in fluorobenzene
at room temperature for 10 h gave 10a and 10b in 82
and 45% yields, respectively. The identity of 9a was
1
confirmed by spectroscopic analysis. The H NMR of
9a shows two methyl peaks at d=2.48 and 2.41 ppm
as singlets. In the 13C NMR spectrum, the carbon
peak of a carbonyl group showed at d=194.0 ppm
and two sp2 carbons at d=144.0 and 127.4 ppm. Fur-
ther confirmation of the identities of the synthesized
compounds 9a–9d and 10a, 10b was obtained by X-
ray crystallographic analysis of compound 9c.[32]
The formation of product 9a is presumed to be ini-
tiated by a Ru(II)-catalyzed decomposition of 1u to
the corresponding ketene intermediate 12 via metal
carbenoid 11 followed by Wolff rearrangement
(Scheme 5).[31] Once formed, ketene 12 would under-
go nucleophilic addition by a chlorine atom of the
oxalyl chloride to give the final product 9a through
extrusion of CO2 and CO from intermediate 13. The
possibility of formation of intermediate 13 could be
Scheme 6.
deduced from oxalates generated by the known reac- phenylboronic acid formed 15 in 64% yield. Impor-
tion between epoxide and oxalyl chloride.[33]
tantly, reaction of 2a with 1.1 equivalents of 3-me-
As an application of this methodology, we attempt- thoxyphenylboronic acid in refluxing aqueous THF
ed the conversion of the synthesized compounds 2a, for 30 h provided product 16 in 68% yield, with high
9b, and 9c to new small molecules using the Suzuki chemoselectivity. Formation of compound 16 was con-
1
reactions, as shown in Scheme 6. Reaction of 2a with firmed by H and 13C NMR spectroscopy. Further, it
2.5 equivalents of phenylboronic acid in the presence was supported by the observation of a strong correla-
of PdACHTUNGTRENNUNG(PPh3)4 in refluxing aqueous THF for 30 h gave tion between CH2 at d=2.33 of the cyclohexenone
14 in 72% yield, whereas treatment with 3-methoxy- ring and a singlet proton at d=6.56 of the aromatic
ring in the 2D NOESY spectrum (see the Supporting
Information). In addition, the Suzuki coupling of 9b
and 9c with 2.5 equivalents of phenylboronic acid fur-
nished compounds 17 and 18 in 84 and 80% yields, re-
spectively (Scheme 6). We believe that these synthetic
routes will be widely used to introduce benzene rings
to cyclic and acyclic a,b-unsaturated enones. The
structure of synthesized compound 18 was confirmed
by analysis of spectral data and an X-ray structure de-
termination.[34]
Conclusions
In summary, we describe here the ruthenium(II)-cata-
Scheme 5.
lyzed reactions between diazodicarbonyls and oxalyl
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chloride or oxalyl bromide. These reactions provided General Procedure for the Synthesis of a,b- and b,b-
an efficient and facile means of synthesizing a variety Dibromoenones (3a–3j and 10a, 10b) and Aromatic
of a,b-dihaloenones or b,b-dihaloenones in moderate Compounds (4a–4e)
to good yields. This protocol includes important ad-
To a solution of diazodicarbonyl compound (1.0 mmol) and
vantages such as simple operation, a toxic and harm-
oxalyl bromide (324 mg, 1.5 mmol) in fluorobenzene
ful chlorine- or phosgene-free route, and mild reac-
tion catalysts over the existing methodologies. The
synthesized compounds were further transformed into
new small molecules using the Suzuki reaction.
(3.0 mL) was added RuCl2ACHTNUGTRNEUNG(PPh3)3 (20 mg, 0.02 mmol) at
room temperature. The reaction mixture was stirred at room
temperature for 10 h until the completion of the reaction as
indicated by TLC. The oxalyl bromide and solvent were
evaporated under reduced pressure to give the residue. The
residue was purified by flash column chromatography on
silica gel with n-hexane/EtOAc (20:1) to give the product.
Experimental Section
General Procedure for Suzuki Coupling Reactions
(14–18)
All experiments were carried out under a nitrogen atmos-
phere. Merck pre-coated silica gel plates (Art. 5554) with
a fluorescent indicator were used as analytical TLC. Flash
column chromatography was performed using silica gel 9385
(Merck). 1H and 13C NMR spectra were recorded on
a Varian-VNS (300 and 75 MHz, respectively) spectrometer
in CDCl3 as the solvent chemical shift. IR spectra were re-
corded on a JASCO FTIR 5300 spectrophotometer. Melting
points were measured with a Fisher–Johns melting point ap-
paratus and uncorrected. The HR-MS were carried out at
Korea Basic Science Institute (Daegu) on a Jeol JMS 700
spectrometer. Structural measurements for the complexes
were performed on a Bruker SMART APEX CCD diffrac-
tometer using graphite monochromatized Mo-Ka radiation
(l=0.71073 ꢂ) at Jeonju center of Korea Basic Science In-
stitute.
To a mixture of phenylboronic acid (2.5 mmol), dihalo-
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
the mixture was refluxed for 30 h. The reaction mixture was
quenched with saturated NH4Cl solution (10 mL) and ex-
tracted with ethyl acetate (3ꢃ10 mL). The combined layers
were washed with water (10 mL), dried (MgSO4), and
evaporated under reduced pressure. Flash chromatography
on silica gel using n-hexane/ethyl acetate (10:1) afforded
products.
1H NMR and 13C NMR Data of Synthesized
Compounds (2–4, 9–10 and 14–18)
2,3-Dichloro-5,5-dimethylcyclohex-2-enone
(2a):
Yield:
1
General Procedure for the Synthesis of a,b- and b,b-
Dichloroenones (2a–2r and 9a–9d)
88%; solid; mp 62–648C; H NMR (300 MHz, CDCl3): d=
2.69 (2H, s), 2.42 (2H, s), 1.06 (6H, s); 13C NMR (75 MHz,
CDCl3): d=189.2, 151.4, 135.3, 50.8, 49.0, 33.3, 27.7; IR
(KBr): n=2961, 2878, 1693, 1595, 1464, 1254, 1141, 1019,
945, 854, 600 cmÀ1; HR-MS: m/z=192.0107 (M+), calcd. for
C8H10Cl2O: 192.0109.
2,3-Dichlorocyclohex-2-enone (2b): Yield: 82%; yellowish
solid; mp 58–608C; 1H NMR (300 MHz, CDCl3): d=2.83
(2H, t, J=6.0 Hz), 2.56 (2H, t, J=6.3 Hz), 2.10–2.02 (2H,
m); 13C NMR (75 MHz, CDCl3): d=189.2, 153.6, 130.5, 37.2,
35.4, 21.3; IR (KBr): n=2960, 1688, 1590, 1416, 1262, 1186,
1137, 1013, 874, 790, 560 cmÀ1; HR-MS: m/z=163.9797
(M+), calcd. for C6H6Cl2O: 163.9796.
To a solution of diazodicarbonyl compound (1.0 mmol) and
oxalyl chloride (1.5 mL) was added RuCl2ACHTUNTRGENUNG(PPh3)3 (20 mg,
0.02 mmol) at room temperature. The reaction mixture was
stirred at 508C for 5 h or at room temperature for 10 h until
the completion of the reaction as indicated by TLC. The
oxalyl chloride was evaporated under reduced pressure to
give the residue. The residue was purified by flash column
chromatography on silica gel with n-hexane/EtOAc (20:1)
to give the product.
General Procedure for the Synthesis of a,b-
Dichloroenones in Solvent (2a, 2d and 2f)
2,3-Dichloro-5-methylcyclohex-2-enone (2c): Yield: 76%;
1
liquid; H NMR (300 MHz, CDCl3): d=2.88–2.81 (1H, m),
2.69- 2.53 (2H, m), 2.35–2.12 (2H, m), 1.08 (3H, d, J=
6.3 Hz); 13C NMR (75 MHz, CDCl3): d=189.1, 152.6, 130.3,
45.1, 43.1, 28.9, 20.2; IR (neat): n=2962, 1694, 1593, 1455,
1378, 1242, 1142, 1060, 979, 824, 599 cmÀ1; HR-MS: m/z=
177.9952 (M+), calcd. for C7H8Cl2O: 177.9952.
To a solution of diazodicarbonyl compound (1.0 mmol) and
oxalyl chloride (190 mg, 1.5 mmol) in PhF (3.0 mL) was
added RuCl2ACHTUNGTRENNUNG(PPh3)3 (20 mg, 0.02 mmol) at room tempera-
ture. The reaction mixture was stirred at 508C for 12 h until
the completion of the reaction as indicated by TLC. The
oxalyl chloride was evaporated under reduced pressure to
give the residue. The residue was purified by flash column
chromatography on silica gel with n-hexane/EtOAc (20:1)
to give the product.
2,3-Dichloro-5-isopropylcyclohex-2-enone (2d): Yield:
1
75%; oily liquid; H NMR (300 MHz, CDCl3): d=2.87–2.77
(1H, m), 2.73–2.60 (2H, m), 2.32–2.19 (1H, m), 2.07–1.94
(1H, m), 1.68–1.57 (1H, m), 0.93 (6H, dd, J=6.6, 1.8 Hz);
13C NMR (75 MHz, CDCl3): d=189.5, 153.0, 130.5, 41.2,
40.1, 39.3, 31.5, 19.3; IR (neat): n=2961, 1694, 1595, 1465,
1254, 1147, 1056, 959, 862, 610 cmÀ1
; HR-MS: m/z=
206.0262 (M+), calcd. for C9H12Cl2O: 206.0265.
2,3-Dichloro-5-(furan-2-yl)cyclohex-2-enone (2e): Yield:
64%; clear liquid; 1H NMR (300 MHz, CDCl3): d=7.33
(1H, br s), 6.30–6.29 (1H, m), 6.07–6.06 (1H, m), 3.62–3.53
6
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FULL PAPERS
Ruthenium(II)-Catalyzed Protocol for Preparation of Diverse a,b- and b,b-Dihaloenones
(1H, m), 3.22–3.05 (2H, m), 3.01–2.76 (2H, m); 13C NMR
(75 MHz, CDCl3): d=187.7, 153.8, 151.5, 142.1, 130.8, 110.3,
105.5, 41.4, 39.9, 32.8; IR (neat): n=2988, 1763, 1693, 1593,
1424, 1376, 1243, 1054, 863, 742, 598 cmÀ1; HR-MS: m/z=
229.9899 (M+), calcd. for C10H8Cl2O2: 229.9901.
3,4-Dichloro-1-methylquinolin-2(1H)-one (2m): Yield:
74%; white solid; mp 170–1728C; 1H NMR (300 MHz,
CDCl3): d=8.01 (1H, dd, J=8.1, 1.2 Hz), 7.65–7.59 (1H,
m), 7.39–7.30 (2H, m), 3.77 (3H, s); 13C NMR (75 MHz,
CDCl3): d=157.4, 141.1, 137.6, 131.6, 126.4, 126.1, 123.2,
118.7, 114.4, 31.0; IR (KBr): n=3084, 1654, 1607, 1456,
1334, 1306, 1169, 1073, 952, 845, 748 cmÀ1; HR-MS: m/z=
226.9903 (M+), calcd. for C10H7Cl2NO: 226.9905.
2,3-Dichloro-5-phenylcyclohex-2-enone (2f): Yield: 89%;
1
solid; mp 53–558C; H NMR (300 MHz, CDCl3): d=7.34–
7.29 (2H, m), 7.26–7.23 (1H, m), 7.22–7.16 (2H, m), 3.50–
3.39 (1H, m), 3.10–2.95 (2H, m), 2.90–2.71 (2H, m);
13C NMR (75 MHz, CDCl3): d=188.4, 152.3, 140.7, 130.7,
128.9, 127.5, 126.4, 43.8, 42.8, 39.3; IR (KBr): n=2922, 1689,
1596, 1244, 1145, 1032, 967, 759, 699 cmÀ1; HR-MS: m/z=
240.0106 (M+), calcd. for C12H10Cl2O: 240.0109.
3,4-Dichloro-1-ethylquinolin-2(1H)-one (2n): Yield: 77%;
1
yellow solid; mp 115–1178C; H NMR (300 MHz, CDCl3):
d=7.79 (1H, dd, J=8.4, 1.5 Hz), 7.64–7.58 (1H, m), 7.39
(1H, d, J=8.4 Hz), 7.34–7.23 (1H, m), 4.39 (2H, q, J=
7.2 Hz), 1.36 (3H, t, J=7.2 Hz); 13C NMR (75 MHz,
CDCl3): d=156.8, 141.0, 136.7, 131.5, 126.6, 126.2, 123.0,
119.0, 114.2, 39.0, 12.5; IR (KBr): n=2984, 1652, 1604, 1449,
1341, 1277, 1165, 1084, 998, 841, 747 cmÀ1; HR-MS: m/z=
241.0057 (M+), calcd. for C11H9Cl2NO: 241.0061.
3,4-Dichloro-1-pentylquinolin-2(1H)-one (2o): Yield:
75%; yellow solid; mp 66–688C; 1H NMR (300 MHz,
CDCl3): d=8.01 (1H, dd, J=8.1, 1.2 Hz), 7.63–7.57 (1H,
m), 7.37–7.27 (2H, m), 4.29 (2H, t, J=7.8 Hz), 1.77–1.68
(2H, m), 1.46–1.31 (4H, m), 0.89 (3H, t, J=6.9 Hz);
13C NMR (75 MHz, CDCl3): d=157.0, 141.0, 136.9, 131.5,
126.5, 126.1, 123.0, 119.0, 114.4, 44.0, 29.0, 27.0, 22.3, 13.9;
IR (KBr): n=2947, 2861, 1645, 1603, 1453, 1310, 1161, 1084,
952, 856, 754, 660 cmÀ1; HR-MS: m/z=283.0532 (M+),
calcd- for C14H15Cl2NO: 283.0531.
1-Allyl-3,4-dichloroquinolin-2(1H)-one (2p): Yield: 66%;
white solid; mp 118–1208C; 1H NMR (300 MHz, CDCl3):
d=7.97 (1H, d, J=8.1 Hz), 7.56 (1H, t, J=7.8 Hz), 7.34–
7.26 (2H, m), 5.96–5.83 (1H, m), 5.23–5.06 (2H, m), 4.96–
4.94 (2H, m); 13C NMR (75 MHz, CDCl3): d=156.9, 141.4,
136.8, 131.5, 130.7, 126.3, 125.9, 123.2, 118.7, 117.7, 115.0,
46.0; IR (KBr): n=3081, 1646, 1598, 1442, 1338, 1308, 1160,
1086, 929, 840, 752 cmÀ1; HR-MS: m/z=253.0063 (M+),
calcd. for C12H9Cl2NO: 253.0061.
5-(Benzo[d]ACHTUNGTRENNUNG[1,3]dioxol-5-yl)-2,3-dichlorocyclohex-2-enone
(2g): Yield: 81%; white crystalline solid; mp 118–1208C;
1H NMR (300 MHz, CDCl3): d=6.75 (1H, d, J=7.8 Hz),
6.68–6.63 (2H, m), 5.93 (2H, s), 3.45–3.41 (1H, m), 3.00
(2H, d, J=8.1 Hz), 2.90–2.67 (2H, m); 13C NMR (75 MHz,
CDCl3): d=188.4, 152.3, 148.0, 146.9, 134.6, 130.7, 119.6,
108.5, 106.8, 101.2, 44.2, 43.1, 39.2; IR (KBr): n=2908, 1682,
1596, 1498, 1434, 1357, 1247, 1035, 976, 927, 816, 587 cmÀ1
;
HR-MS: m/z=284.0008 (M+), calcd. for C13H10Cl2O3:
284.0007.
2,3-Dichloro-5-(3,4-dimethoxyphenyl)cyclohex-2-enone
(2h): Yield: 92%; white solid; mp 98–1008C; 1H NMR
(300 MHz, CDCl3): d=6.70 (1H, d, J=7.8 Hz), 6.64–6.63
(1H, m), 6.60–6.59 (1H, m), 3.73 (3H, s), 3.71 (3H, s), 3.35–
3.24 (1H, m), 2.92 (2H, d, J=7.5 Hz), 2.79–2.58 (2H, m);
13C NMR (75 MHz, CDCl3): d=188.4, 152.2, 149.0, 148.2,
133.3, 130.5, 118.2, 111.3, 109.8, 55.8, 44.1, 43.0, 39.0; IR
(KBr): n=2960, 1695, 1595, 1517, 1461, 1244, 1149, 1024,
977, 810 cmÀ1; HR-MS: m/z=300.0318 (M+), calcd. for
C14H14Cl2O3: 300.0320.
2,3-Dichloro-1H-phenalen-1-one (2i): Yield: 67%; yellow
1
solid; mp 155–1578C; H NMR (300 MHz, CDCl3): d=8.68
(1H, d, J=7.5 Hz), 8.29 (1H, d, J=7.5 Hz), 8.22 (1H, d, J=
8.1 Hz), 8.08 (1H, d, J=8.1 Hz), 7.76 (1H, t, J=7.8 Hz),
7.66 (1H, t, J=7.8 Hz); 13C NMR (75 MHz, CDCl3): d=
177.0, 144.5, 135.9, 133.2, 132.4, 131.8, 131.0, 130.6, 127.8,
127.3, 126.8, 126.1, 125.6; IR (KBr): n=2926, 1644, 1569,
1390, 1297, 1150, 994, 901, 837, 770 cmÀ1; HR-MS: m/z=
247.9796 (M+), calcd. for C13H6Cl2O: 247.9796.
1-Benzyl-3,4-dichloroquinolin-2(1H)-one (2q): Yield:
68%; yellowish solid; mp 162–1648C; 1H NMR (300 MHz,
CDCl3): d=7.98 (1H, d, J=8.1 Hz), 7.43 (1H, t, J=8.1 Hz),
7.28–7.14 (7H, m), 5.53 (2H, s); 13C NMR (75 MHz,
CDCl3): d=157.7, 142.5, 141.9, 137.1, 135.4 131.6, 128.9,
127.6, 126.6, 126.5, 123.3, 119.0, 115.3, 47.5; IR (KBr): n=
2924, 1645, 1639, 1493, 1451, 1308, 1163, 1095, 955, 842,
2,3-Dichlorocyclopent-2-enone (2j): Yield: 57%; liquid;
1H NMR (300 MHz, CDCl3): d=2.89 (2H, t, J=4.8 Hz),
2.65 (2H, t, J=4.8 Hz); 13C NMR (75 MHz, CDCl3): d=
196.8, 133.3, 132.6, 33.9, 31.8; IR (neat): n=2930, 1725,
1603, 1435, 1296, 1230, 1066, 968, 888, 818, 569 cmÀ1; HR-
MS: m/z=149.9636 (M+), calcd. for C5H4Cl2O: 149.9639.
2,3-Dichloro-1H-inden-1-one (2k): Yield: 78%; yellow
solid; mp 77–798C; 1H NMR (300 MHz, CDCl3): d=7.79
(1H, d, J=7.5 Hz), 7.70–7.63 (2H, m) 7.57 (1H, d, J=
7.5 Hz); 13C NMR (75 MHz, CDCl3): d=158.4, 150.2, 146.2,
134.5, 133.8, 133.7, 131.1, 123.5, 123.2; IR (KBr): n=2926,
1726, 1600, 1542, 1462, 1274, 1200, 1021, 911, 810, 745, 695,
739 cmÀ1
;
HR-MS: m/z=303.0215 (M+), calcd. for
C16H11Cl2NO: 303.0218.
3,4-Dichloro-1-(4-methylbenzyl)quinolin-2(1H)-one (2r):
Yield: 66%; white solid; mp 165–1678C; 1H NMR
(300 MHz, CDCl3): d=7.95 (1H, d, J=8.1 Hz), 7.41 (1H, t,
J=8.1 Hz), 7.28–7.17 (2H, m), 7.06–7.00 (4H, m), 5.47 (2H,
s), 2.21 (3H, s); 13C NMR (75 MHz, CDCl3): d=157.6,
141.6, 137.3, 137.1, 132.3, 131.6, 129.5, 126.6, 126.4, 126.0,
123.2, 118.9, 115.3, 47.2, 21.0; IR (KBr): n=2944, 1651,
1604, 1513, 1449, 1311, 1161, 1092, 955, 844, 757 cmÀ1; HR-
MS: m/z=317.0371 (M+), calcd. for C17H13Cl2NO: 317.0374.
2,3-Dibromo-5,5-dimethylcyclohex-2-enone (3a): Yield:
63%; crystalline solid; mp 82–848C; 1H NMR (300 MHz,
CDCl3): d=2.82 (2H, s), 2.45 (2H, s), 1.07 (6H, s);
13C NMR (75 MHz, CDCl3): d=189.0, 148.2, 126.7, 52.6,
51.0, 34.7, 28.0; IR (KBr): n=2959, 1689, 1582, 1463, 1413,
1236, 1139, 1002, 927, 755 cmÀ1; HR-MS: m/z=279.9096
(M+), calcd. for C8H10Br2O: 279.9098.
593 cmÀ1
;
HR-MS: m/z=197.9635 (M+), calcd. for
C9H4Cl2O: 197.9639.
2,3-Dichlorocyclohept-2-enone (2l): Yield: 51%; liquid;
1H NMR (300 MHz, CDCl3): d=2.94 (2H, s), 2.70 (2H, s),
1.87–1.85 (4H, m); 13C NMR (75 MHz, CDCl3): d=194.5,
150.6, 132.6, 40.8, 37.4, 24.2, 20.7; IR (neat): n=2944, 1689,
1580, 1452, 1320, 1244, 1176, 1062, 966, 803, 560 cmÀ1; HR-
MS: m/z=177.9951 (M+), calcd. for C7H8Cl2O: 177.9952.
Adv. Synth. Catal. 0000, 000, 0 – 0
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ÞÞ
These are not the final page numbers!

FULL PAPERS
Krishna Bahadur Somai Magar and Yong Rok Lee
2,3-Dibromo-1H-phenalen-1-one (3b): Yield: 52%; yellow
solid; mp 164–1668C; H NMR (300 MHz, CDCl3): d=8.62
d=8.01 (1H, dd, J=8.1, 1.2 Hz), 7.45–7.39 (1H, m), 7.24–
7.13 (7H, m), 5.53 (2H, s); 13C NMR (75 MHz, CDCl3): d=
157.6, 138.6, 137.6, 135.5, 131.7, 130.1, 129.0, 127.6, 126.6,
123.5, 122.7, 120.7, 115.3, 48.0; IR (KBr): n=1763, 1634,
1490, 1450, 1378, 1243, 1159, 1061, 930, 740 cmÀ1; HR-MS:
m/z=390.9203 (M+), calcd. for C16H11Br2NO: 390.9207.
3,4-Dibromo-1-(4-methylbenzyl)quinolin-2(1H)-one (3j):
Yield: 70%; white solid; mp 168–1708C; 1H NMR
(300 MHz, CDCl3): d=8.00 (1H, dd, J=8.1, 1.2 Hz), 7.44–
7.39 (1H, m), 7.26–7.15 (2H, m), 7.06–7.00 (4H, m), 5.48
(2H, s), 2.21 (3H, s); 13C NMR (75 MHz, CDCl3): d=157.6,
138.5, 137.6, 137.3, 132.4, 131.6, 130.0, 129.5, 126.6, 123.4,
122.7, 120.7, 115.4, 47.7, 21.0; IR (KBr): n=1645, 1449,
1308, 1164, 1080, 927, 756 cmÀ1; HR-MS: m/z=404.9361
(M+), calcd. for C17H13Br2NO: 404.9364.
1
(1H, d, J=7.5 Hz), 8.28 (1H, d, J=7.5 Hz), 8.17 (1H, d, J=
7.5 Hz), 8.04 (1H, d, J=8.1 Hz), 7.22 (1H, t, J=7.8 Hz),
7.59 (1H, t, J=7.8 Hz); 13C NMR (75 MHz, CDCl3): d=
176.7, 141.9, 135.7, 134.4, 133.3, 132.8, 132.3, 131.8, 131.2,
127.5, 127.3, 127.0, 117.3; IR (KBr): n=3059, 2925, 1640,
1567, 1435, 1384, 1295, 1241, 1141, 980, 832, 767, 603 cmÀ1
;
HR-MS: m/z=335.8784 (M+), calcd. for C13H6Br2O:
335.8785.
2,3-Dibromo-1H-inden-1-one (3c): Yield: 40%; yellow
1
solid; mp 90–928C; H NMR (300 MHz, CDCl3): d=7.46–
7.41 (2H, m), 7.30–7.25 (1H, m), 7.19–7.16 (1H, m);
13C NMR (75 MHz, CDCl3): d=186.6, 146.3, 142.5, 134.4,
130.2, 129.9, 123.0, 122.4, 121.1; IR (KBr): n=2930, 1719,
1608, 1547, 1452, 1368, 1213, 1095, 576, 691, 499 cmÀ1; HR-
MS: m/z=285.8626 (M+), calcd. for C9H4Br2O: 285.8629.
3,4-Dibromo-2H-chromen-2-one (3d): Yield: 43%; reddish
solid; mp 78–808C; 1H NMR (300 MHz, CDCl3): d=7.86
(1H, dd, J=8.1, 1.2 Hz), 7.63–7.57 (1H, m), 7.38–7.31 (2H,
m); 13C NMR (75 MHz, CDCl3): d=151.1, 142.7, 133.0,
128.9, 125.5, 119.6, 117.0, 116.8, 116.6; IR (KBr): n=3084,
1729, 1596, 1540, 1451, 1277, 1177, 990, 753, 648 cmÀ1; HR-
MS: m/z=301.8576 (M+), calcd. for C9H4Br2O2: 301.8578.
3,4-Dibromo-1-methylquinolin-2(1H)-one (3e): Yield:
62%; white solid; mp 140–1428C; 1H NMR (300 MHz,
CDCl3): d=8.04 (1H, dd, J=8.1, 1.2 Hz), 7.64–7.58 (1H,
m), 7.35–7.25 (2H, m), 3.76 (3H, s); 13C NMR (75 MHz,
CDCl3): d=157.2, 138.0, 137.8, 131.7, 129.8, 123.4, 122.7,
120.3, 114.4, 31.3; IR (KBr): n=3090, 1648, 1452, 1307,
1165, 1064, 957, 747, 657 cmÀ1; HR-MS: m/z=314.8897
(M+), calcd. for C10H7Br2NO: 314.8894.
3,4-Dibromo-1-ethylquinolin-2(1H)-one (3f): Yield: 64%;
white solid; mp 100–1028C; 1H NMR (300 MHz, CDCl3):
d=8.00 (1H, d, J=8.1 Hz), 7.58–7.52 (1H, m), 7.30 (1H, d,
J=8.4 Hz), 7.21 (1H, d, J=8.1 Hz), 4.33 (2H, q, J=7.2 Hz),
1.36 (3H, t, J=7.2 Hz); 13C NMR (75 MHz, CDCl3): d=
156.7, 137.8, 137.1, 131.6, 130.2, 123.2, 122.8, 120.6, 114.3,
39.4, 12.4; IR (KBr): n=2977, 1643, 1455, 1263, 1160, 1073,
990, 899, 744, 457 cmÀ1; HR-MS: m/z=328.9052 (M+), calcd.
for C11H9Br2NO: 328.9051.
3-Bromophenol (4a): Yield: 68%; liquid; 1H NMR
(300 MHz, CDCl3): d=6.99–6.94 (2H, m), 6.89 (1H, s),
6.66–6.62 (1H, m), 5.61 (1H, br s); 13C NMR (75 MHz,
CDCl3): d=155.7, 130.8, 124.1, 122.7, 118.7, 114.2; IR
(neat): n=3393, 1698, 1651, 1585, 1445, 1299, 1239, 1063,
860, 770, 676 cmÀ1; HR-MS: m/z=171.9522 (M+), calcd. for
C6H5BrO: 171.9524.
3-Bromo-5-isopropylphenol (4b): Yield: 70%; whitish
solid; mp 53–558C; 1H NMR (300 MHz, CDCl3): d=7.00
(1H, s), 6.80 (1H, s), 6.61 (1H, s), 4.83 (1H, br s), 2.84–2.74
(1H, s), 1.20 (3H, s), 1.18 (3H, s); 13C NMR (75 MHz,
CDCl3): d=156.1, 152.5, 122.5, 122.3, 116.1, 112.4, 34.0, 23.6;
IR (KBr): n=3399, 1703, 1596, 1441, 1268, 1177, 1096, 958,
847, 792, 692 cmÀ1; HR-MS: m/z=213.9994 (M+), calcd. for
C9H11BrO: 213.9993.
5-Bromobiphenyl-3-ol (4c): Yield: 72%; yellowish solid;
mp 48–508C; 1H NMR (300 MHz, CDCl3): d=7.52–7.49
(2H, m), 7.44–7.35 (3H, m), 7.30–7.29 (1H, m), 6.98–6.95
(2H, m), 5.00 (1H, br s); 13C NMR (75 MHz, CDCl3): d=
156.5, 144.3, 139.3, 128.8, 128.0, 127.0, 123.0, 122.7, 117.4,
113.1; IR (KBr): n=3310, 1595, 1474, 1414, 1300, 1192, 909,
849, 759, 693 cmÀ1; HR-MS: m/z=247.9838 (M+), calcd. for
C12H9BrO: 247.9837.
5-Bromo-3’,4’-dimethoxybiphenyl-3-ol (4d): Yield: 65%;
1
whitish solid: mp 123–1258C; H NMR (300 MHz, CDCl3):
d=7.17 (1H, s), 7.00–6.94 (2H, m), 6.89–6.81 (3H, m), 5.70
(1H, br s), 3.83 (3H, s), 3.82 (3H, s); 13C NMR (75 MHz,
CDCl3): d=156.7, 149.0, 148.9, 144.0, 132.4, 123.0, 122.2,
119.5, 117.0, 112.8, 111.5, 110.2, 56.0; IR (KBr): n=3420,
1763, 1600, 1567, 1517, 1463, 1246, 1144, 1054, 851, 743,
3,4-Dibromo-1-pentylquinolin-2(1H)-one (3g): Yield:
74%; white solid; mp 80–828C; 1H NMR (300 MHz,
CDCl3): d=8.01 (1H, dd, J=8.1, 1.2 Hz), 7.59–7.53 (1H,
m), 7.30–7.09 (2H, m), 4.25 (2H, q, J=7.8 Hz), 1.73–1.63
(2H, m), 1.42–1.29 (4H, m), 0.85 (3H, t, J=6.9 Hz);
13C NMR (75 MHz, CDCl3): d=157.0, 137.8, 137.4, 131.6,
130.2, 123.2, 122.9, 120.6, 114.5, 44.4, 29.0, 27.0, 22.3, 14.0;
IR (KBr): n=2940, 1647, 1457, 1256, 1159, 1069, 926, 744,
606 cmÀ1
C14H13BrO3: 308.0048.
3-(Benzo[d][1,3]dioxol-5-yl)-5-bromophenol (4e): Yield:
;
HR-MS: m/z=308.0052 (M+), calcd. for
AHCTUNGTRENNUNG
62%; whitish solid; mp 88–908C; 1H NMR (300 MHz,
CDCl3): d=7.21–7.20 (1H, m), 6.97–6.92 (3H, m), 6.87–6.82
(2H, m), 6.00 (2H, s), 5.17 (1H, s); 13C NMR (75 MHz,
CDCl3): d=156.3, 148.1, 147.5, 144.0, 133.5, 123.0, 122.6,
120.7, 117.1, 112.8, 108.6, 107.4, 101.2; IR (KBr): n=3303,
1570, 1474, 1315, 1238, 1042, 935, 857, 637 cmÀ1; HR-MS: m/
z=291.9734 (M+), calcd. for C13H9BrO3: 291.9735.
457 cmÀ1
;
HR-MS: m/z=370.9519 (M+), calcd. for
C14H15Br2NO: 370.9520.
1-Allyl-3,4-dibromoquinolin-2(1H)-one (3h): Yield: 66%;
white solid; mp 110–1128C; 1H NMR (300 MHz, CDCl3):
d=8.03 (1H, dd, J=8.1, 1.2 Hz), 7.56–7.50 (1H, m), 7.32–
7.19 (2H, m), 5.94–5.81 (1H, m), 5.19 (1H, d, J=10.2 Hz),
5.08 (1H, d, J=17.4 Hz), 4.94–4.93 (2H, m); 13C NMR
(75 MHz, CDCl3): d=157.0, 138.3, 137.5, 131.6, 130.8, 130.0,
123.4, 122.7, 120.6, 118.0, 115.1, 46.5; IR (KBr): n=1638,
1440, 1303, 1160, 1077, 924, 753, 657 cmÀ1; HR-MS: m/z=
340.9047 (M+), calcd. for C12H9Br2NO: 340.9051.
4,4-Dichloro-3-methylbut-3-en-2-one (9a): Yield: 83%;
1H NMR (300 MHz, CDCl3): d=2.48 (3H, s), 2.41 (3H, s);
13C NMR (75 MHz, CDCl3): d=194.0, 144.0, 127.4, 29.8,
25.0; IR (neat): n=2925, 1696, 1577, 1423, 1359, 1217, 1126,
1037, 971, 760, 583 cmÀ1; HR-MS: m/z=151.9793 (M+),
calcd. for C5H6Cl2O: 151.9796.
1-Benzyl-3,4-dibromoquinolin-2(1H)-one (3i): Yield: 65%;
white solid; mp 184–1868C; 1H NMR (300 MHz, CDCl3):
8
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Adv. Synth. Catal. 0000, 000, 0 – 0
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These are not the final page numbers!

FULL PAPERS
Ruthenium(II)-Catalyzed Protocol for Preparation of Diverse a,b- and b,b-Dihaloenones
3,3-Dichloro-1,2-diphenylprop-2-en-1-one (9b): Yield:
191.4, 166.9, 160.9, 154.1, 130.3, 112.5, 111.3, 106.5, 55.5,
50.9, 41.6, 32.4, 27.9; IR (neat): n=2959, 1676, 1592, 1486,
1349, 1290, 1233, 1131, 1038, 922, 778, 698 cmÀ1; HR-MS:
m/z=264.0919 (M+), calcd. for C15H17ClO2: 264.0917.
1
93%; oily liquid; H NMR (300 MHz, CDCl3): d=8.06–8.02
(2H, m), 7.60–7.44 (5H, m), 7.40–7.29 (3H, m); 13C NMR
(75 MHz, CDCl3): d=192.0, 139.2, 134.4, 134.2, 133.2, 129.7,
129.0, 128.9, 128.6, 128.2, 121.4; IR (neat): n=3044, 1681,
1585, 1446, 1251, 1050, 757, 690, 615 cmÀ1; HR-MS: m/z=
276.0108 (M+), calcd. for C15H10Cl2O: 276.0109.
1,2,3,3-Tetraphenylprop-2-en-1-one (17): Yield: 84%;
1
solid; mp 150–1528C; H NMR (300 MHz, CDCl3): d=7.85–
7.82 (2H, m), 7.28–7.25 (1H, m), 7.21–7.16 (2H, m), 7.09–
7.06 (4H, m), 7.04–7.01 (8H, m), 6.99–6.97 (3H, m);
13C NMR (75 MHz, CDCl3): d=198.8, 144.7, 141.6, 140.8,
139.5, 138.6, 137.6, 132.6, 131.0, 130.0, 129.8, 129.6, 128.4,
128.3, 128.2, 127.9, 127.8, 127.5, 127.2; IR (KBr): n=3074,
2926, 1660, 1595, 1488, 1443, 1315, 1258, 1163, 1072, 955,
754, 696, 592 cmÀ1; HR-MS: m/z=360.1511 (M+), calcd. for
C27H20O: 360.1514.
1,2-Bis(4-methoxyphenyl)-3,3-diphenylprop-2-en-1-one
(18): Yield: 80%; yellowish crystalline solid; mp 165–1678C;
1H NMR (300 MHz, CDCl3): d=7.91 (2H, d, J=8.4 Hz),
7.17–7.09 (10H, m), 6.99 (2H, d, J=8.4 Hz), 6.78 (2H, d,
J=8.4 Hz), 6.64 (2H, d, J=8.4 Hz), 3.77 (3H, s), 3.69 (3H,
s); 13C NMR (75 MHz, CDCl3): d=197.5, 163.0, 158.5, 142.7,
142.0, 141.3, 139.2, 132.0, 131.1, 131.0, 131.0, 130.6, 129.8,
128.0, 127.8, 127.6, 127.7, 113.7, 113.5, 55.3, 55.0; IR (KBr):
n=3034, 2930, 2837, 1658, 1598, 1509, 1444, 1256, 1172,
1028, 836, 766, 702, 554 cmÀ1; HR-MS: m/z=420.1726 (M+),
calcd. for C29H24O3: 420.1725.
3,3-Dichloro-1,2-bis(4-methoxyphenyl)prop-2-en-1-one
(9c): Yield: 74%; white crystalline solid; mp 114–1168C;
1H NMR (300 MHz, CDCl3): d=7.95 (2H, d, J=9.0 Hz),
7.43 (2H, d, J=9.0 Hz), 6.93 (2H, d, J=9.0 Hz), 6.86 (2H,
d, J=9.0 Hz), 3.83 (3H, s), 3.76 (3H, s); 13C NMR (75 MHz,
CDCl3): d=191.0, 164.3, 160.0, 139.0, 132.2, 129.7, 127.5,
125.8, 119.8, 114.2, 114.0, 55.5, 55.2; IR (KBr): n=2934,
1653, 1599, 1507, 1460, 1257, 1166, 1023, 850, 555 cmÀ1; HR-
MS: m/z=336.0317 (M+), calcd. for C17H14Cl2O3: 336.0320.
Ethyl 3,3-dichloro-2-phenylacrylate (9d): Yield: 53%;
1
liquid; H NMR (300 MHz, CDCl3): d=7.40–7.32 (5H, m),
3.99 (2H, q, J=7.2 Hz), 0.92 (3H, t, J=7.2 Hz); 13C NMR
(75 MHz, CDCl3): d=162.5, 142.0, 137.0, 129.8, 128.3, 128.1,
122.5, 62.3, 13.3; IR (neat): n=2984, 1730, 1588, 1446, 1367,
1259, 1054, 910, 840, 760, 705, 622 cmÀ1; HR-MS: m/z=
244.0056 (M+), calcd. for C11H10Cl2O2: 244.0058
3,3-Dibromo-1,2-diphenylprop-2-en-1-one (10a): Yield:
1
82%; solid; mp 53–558C; H NMR (300 MHz, CDCl3): d=
8.04–8.01 (2H, m), 7.61–7.55ACTHNUGRTNEUNG(1H, m), 7.51–7.45 (4H, m),
7.38–7.31 (3H, m); 13C NMR (75 MHz, CDCl3): d=192.7,
146.6, 135.5, 134.2, 133.9, 129.9, 129.0, 128.8, 128.7, 128.1,
90.9; IR (KBr): n=3059, 1671, 1594, 1489, 1447, 1311, 1259,
1173, 1053, 903, 756, 694, 613, 554 cmÀ1; HR-MS: m/z=
363.9096 (M+), calcd. for C15H10Br2O: 363.9098.
Acknowledgements
This research was supported by Basic Science Research Pro-
gram through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and
Technology (2012R1A1A4A01009620).
Ethyl 3,3-dibromo-2-phenylacrylate (10b): Yield: 45%;
liquid; 1H NMR (300 MHz, CDCl3): d=7.37
ACTHNUGRTENUNG(5H, m), 4.25
(2H, q, J=7.2 Hz), 1.28 (3H, t, J=7.2 Hz); 13C NMR
(75 MHz, CDCl3): d=165.8, 141.5, 135.7, 129.6, 128.5, 128.1,
121.1, 62.2, 14.0; IR (neat): n=2988, 1734, 1580, 1450, 1368,
1252, 1057, 919, 839, 767, 627 cmÀ1; HR-MS: m/z=331.9050
(M+), calcd. for C11H10Br2O2: 331.9048..
References
5,5-Dimethyl-2,3-diphenylcyclohex-2-enone (14): Yield:
72%; liquid; 1H NMR (300 MHz, CDCl3): d=7.53–7.50
(3H, m), 7.40–7.38 (4H, m), 7.24–7.18 (1H, m), 6.91–6.82
(2H, m), 2.64 (2H, s), 2.34 (2H, s), 1.18 (6H, s); 13C NMR
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755, 694, 508 cmÀ1; HR-MS: m/z=276.1512 (M+), calcd, for
C20H20O: 276.1514.
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12 Ruthenium(II)-Catalyzed Protocol for Preparation of
Diverse a,b- and b,b-Dihaloenones from Diazodicarbonyls
Adv. Synth. Catal. 2014, 356, 1 – 12
Krishna Bahadur Somai Magar, Yong Rok Lee*
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