Rh(II) Catalyzed three-component reactions of diazoacetates with benzenemethanol and indane-1, 2, 3-triones

Article abstract of DOI:10.2174/157017810790796282

A facile synthesis of 2-substituted-2-hydroxyindane-1,3-diones is reported via the reaction of diazoacetates with benzenemethanol and indane-1,2,3-triones catalyzed by dirhodium acetate.

Full text of DOI:10.2174/157017810790796282

106
Letters in Organic Chemistry, 2010, 7, 106-109
Rh(II) Catalyzed Three-Component Reactions of Diazoacetates with
Benzenemethanol and Indane-1, 2, 3-Triones
Xin Guo, Jingjing Wang, Liping Yang and Wenhao Hu*
Department of Chemistry, East China Normal University, Shanghai 200062, P. R. of China
Received May 14, 2008: Revised December 21, 2009: Accepted January 07, 2010
Abstract: A facile synthesis of 2-substituted-2-hydroxyindane-1,3-diones is reported via the reaction of diazoacetates
with benzenemethanol and indane-1,2,3-triones catalyzed by dirhodium acetate.
Keywords: Multi-component reaction, diazo compounds, carbenoids, oxonium ylide, dirhodium acetate, indane-1, 3-diones.
INTRODUCTION
molar ratio, and the results are summarized in Table 1. The
best yield of 69% was obtained when 1.5 equivalent of both
1a and benzenemethanol (2) were used (Table 1, entry 3).
However, significant amount of the O-H insertion side
product 5 occurred due to large excess of both the diazo
compound and the alcohol. In order to decrease the
formation of 5, we reduced the amount of the diazo
compound 1a to a substrate ratio of 1a:2:3a= 1.1:1.5:1. The
desired three-component product 4a was isolated with
similar good yield (65%) and the O-H insertion side product
5 was suppressed to less than 10 % (Table 1, entry 6). The
structure of product 4a was determined based on its
spectroscopic and analytical data and confirmed by single
crystal X-ray analysis. The X-ray structure confirmed that
the nucleophilic attacking to the indane-1, 2, 3-trione
specifically occurred at the 2-position (Fig. 1).
It is well known that metal carbenoids react with
heteroatoms to form onium ylides [1]. The chemistry of
onium ylides is an area of continuing interest [2].
Phosphorus, sulfur, ammonium, carbonyl and oxonium
ylides have been widely utilized in organic synthesis [3].
Previously, we reported novel three component reactions, in
which, an alcoholic/ ammonium ylide in situ generated from
a diazo compound and an alcohol/amine in the presence of
rhodium acetate can be trapped by carbonyls [4], imines [4b,
5] and azodicarboxylates [6]. As for the alcoholic ylide
trapping process, the reactions were successful when
electron-deficient aldehydes and isatins were used due to a
competing process from an intramolecular proton transfer of
the alcoholic ylide leading to an O-H insertion side product
[4]. To extend the scope of this method, we envision that
indane-1, 2, 3-triones would serve as good trapping reagents
for the reaction, because the strong electrophilicity of the 2-
carbonyl functionality of the 1, 2, 3-triones made them
widely used in aldol type reactions [7]. Trapping of the
alcoholic ylide with indane-1, 2, 3-triones would provide an
easy entry to polyfunctional 2-hydroxyindane-1, 3-diones
with a C-C and C-O bond formation in one step (Scheme 1).
Having established the preferred reaction conditions, we
applied the synthetic strategy to
diazoacetates and indane-1,
a variety of aryl
2, 3-triones (Table 2) [8]. Reactions of aryl diazoacetates
bearing either an electron-donating group or an electron-
withdrawing group on the aromatic ring at the para-position
gave the products with similar yield (Table 2, entries 2, 3).
O
O
OH
N2
BnO
OBn
COOMe
Rh2(OAc)4
CH2Cl2
R2
R1
+
BnOH +
O
+
R1
COOR3
R3OOC
Ph
O
O
1
2
3
4
5
Scheme 1. The three-component reaction for 2-substituted-2-hydroxyindane-1, 3-diones formation.
RESULTS AND DISCUSSION
The aryl diazoacetates with the ortho-substituents gave
lower yields than those with the meta- and para-substituents
(Table 2, entries 2-5). The low yield is probably due to steric
effects of the ortho-substituents which slow down the
desired nucleophilic addition process. Decreased yields were
also obtained with the use of indane-1, 2, 3-triones bearing
substituents on the ortho-position of the aromatic ring (Table
2, entries 6-9).
Methyl phenyldiazoacetate (1a) was used as a standard
substrate to demonstrate the strategy. The reaction was first
carried out in refluxing CH2Cl2 with different substrate
*Address correspondence to this author at the Department of Chemistry,
East China Normal University, Shanghai 200062, P. R. of China; Fax:
+86(21)62233176; E-mail: whu@chem.ecnu.edu.cn
1570-1786/10 $55.00+.00
© 2010 Bentham Science Publishers Ltd.

Rhodium Catalyzed Three-Component Reactions
Letters in Organic Chemistry, 2010, Vol. 7, No. 2
107
Table 1. Reaction of Methyl Phenyldiazoacetate with BnOH and Indane-1, 2, 3-Trione with Different Substrate Molar Ratioa
O
O
OH
N2
BnO
Ph
Rh2(OAc)4
CH2Cl2
+
BnOH +
O
Ph
COOMe
MeOOC
O
O
1a
2
3a
4a
Entry
1a : 2 : 3a
Yield of 4a (%)b
1
2
3
4
5
6
7
1ꢀ1ꢀ1
1.2ꢀ1.2ꢀ1
1.5ꢀ1.5ꢀ1
2ꢀ2ꢀ1
27
41
69
67
38
65
64
1.1ꢀ1.2ꢀ1
1.1ꢀ1.5ꢀ1
1.1ꢀ2ꢀ1
aThe reaction of methyl phenyldiazoacetate with BnOH and indane-1,2,3-trone was carried out in refluxing CH2Cl2 for 1 h. bIsolated yield after column chromatography purification.
We were gratified to find that the reaction gave 56%
yield when EDA (ethyl diazoacetate ) was used instead of
aryl diazoacetates (Scheme 2). In contrast, in the reactions
of ammonium or alcoholic ylide with aldehydes, much
lower yields were obtained when EDA was employed [4a,
4c].
A reaction mechanism shown in Scheme 3 is similar to
that we proposed previously [4d]. The reaction initially
forms a free oxonium ylide 6 or a metal associated ylide 7
from aryldiazoacetate 1a and benzenemethanol catalyzed by
Rh2(OAc)4. Nucleophilic addition of the ylide 5 or 6 to the
indane-1, 2, 3-triones would produce intermediate adduct 8
or 9. Product 4a would be subsequently formed by a
“delayed proton transfer” process.
In summary, we report here dirhodium acetate catalyzed
three-component reactions of diazo compounds with
benzenemethanol and indane-1, 2, 3-triones to give
polyfunctional 2-hydroxyindane-1, 3-diones in a single step.
ACKNOWLEDGEMENT
We are grateful for financial support from the NSFC
(Grant Nos. 20932003, 20772033) and sponsorship from
Fig. (1). Crystal structure of compound 4a.
Table 2. Reaction of Different Aryl Diazoacetates with BnOH and Substituted Indane-1, 2, 3-Trionesa
R
O
O
OH
N2
BnO
Ar
Rh2(OAc)4
CH2Cl2
R
+
BnOH +
O
Ar
COOMe
MeOOC
O
O
1
2
3
4
Entry
1
3
Product
Yield(%)b
1
2
1a, Ar=Ph
1b, Ar=p-MeOC6H4
3a, R=H
4a
4b
65
54
3a

108 Letters in Organic Chemistry, 2010, Vol. 7, No. 2
Guo et al.
(Table 2). Contd…..
Entry
1
3
Product
Yield(%)b
3
4
5
6
7
8
9
1c, Ar=p-BrC6H4
3a
4c
4d
4e
4f
53
55
26
24
30
29
21
1d, Ar=m-BrC6H4
3a
1e, Ar=o-ClC6H4
3a
1a
1a
1a
1a
3b, R= F
3c, R=Cl
3d, R=Br
3e, R=Me
4g
4h
4i
aThe reaction was conducted in refluxing CH2Cl2 for 1h with substrate molar ratio of 1:2:3=1.1:1.5:1. bIsolated yield after column chromatography purification.
O
O
OH
N2
BnO
H
Rh2(OAc)4
CH2Cl2
+
BnOH +
O
H
COOEt
EtOOC
O
O
1f
2
3a
4j
Scheme 2. The reaction of EDA with BnOH and indane-1, 2, 3-trione.
Ph
H
BnO
Ph
MeOOC
ORhLn
O
LnRh
C
O
COOMe
Bn
BnOH
2
COOMe
Ph
H
N2
+
O
3a
6
Rh(II)
O
O
8
1a
nucleophilic
addition
or
H
O
Ph
C
BnO
Ph
O
O
COOMe
+
RhLn
MeOOC
O
3a
H
Bn
O
9
7
proton transfer
-RhLn
''delayed proton transfer''
BnO
Ph
OH
O
Ph
HC COOMe
OBn
MeOOC
O
5
4a
Scheme 3. The proposed mechanism for the three-component reaction.
Shanghai (Grant Nos. 10XD1401700, 09JC1404901,
51K03117).
1,2,3-trione (89.1 mg, 0.5 mmol) was added methyl
phenyldiazoacetate 1a (96.8 mg, 0.55 mmol) in 5 mL of
CH2Cl2 over 1 h via a syringe pump. The reaction mixture
was cooled to r.t., and the solvent was removed. The crude
product was purified by flash chromatography on silica gel
by using 10% EtOAc–light PE as eluents to give a white
solid 4a (135.4 mg, 0.33 mmol) with 65% yield. Analytical
Typical Procedure of the Three-component Reaction
To a refluxing CH2Cl2 (20 mL) solution of Rh2(OAc)4
(2.4 mg, 1 mol%), BnOH (75 ꢀL, 0.75mmol) and indane-

Rhodium Catalyzed Three-Component Reactions
Letters in Organic Chemistry, 2010, Vol. 7, No. 2
109
data of 4a: 1H NMR (500 MHz, CDCl3): ꢀ = 8.00-7.75 (m, 4
H), 7.50-7.00 (m, 8 H), 6.87-6.75 (m, 2 H), 4.82 (d, J = 12.2
Hz, 1 H ), 4.44 (d, J = 12.2 Hz, 1 H), 3.88 (s, 3 H); 13C NMR
(125 MHz, CDCl3): ꢀ = 197.72, 195.38, 170.67, 142.53,
141.91, 137.84, 135.80, 135.68, 131.17, 129.23, 128.49,
128.06, 128.04, 127.11, 126.10, 123.30, 123.21, 87.31, 80.13,
68.58, 52.91.
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a dual functional catalyst for three-