Synthesis of water-tolerant indium homoenolate in aqueous media and its application in the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling with acid chloride

Article abstract of DOI:10.1021/ja106925f

The first water-tolerant, ketone-type indium homoenolate was synthesized via the oxidative addition of In/InCl₃ to enones. The reaction proceeds exclusively in aqueous media. Both indium and indium(III) chloride are necessary for the smooth conversion of the reaction. Similar results were obtained when InCl or InCl₂ was used in place of In/InCl₃. The synthetic utility of the indium homoenolate was demonstrated through the synthesis of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of indium homoenolate with acid chloride.

Full text of DOI:10.1021/ja106925f

Published on Web 10/21/2010
Synthesis of Water-Tolerant Indium Homoenolate in Aqueous Media and Its
Application in the Synthesis of 1,4-Dicarbonyl Compounds via
Palladium-Catalyzed Coupling with Acid Chloride
Zhi-Liang Shen, Kelvin Kau Kiat Goh,† Hao-Lun Cheong,† Colin Hong An Wong, Yin-Chang Lai,
Yong-Sheng Yang, and Teck-Peng Loh*
DiVision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang
Technological UniVersity, Singapore 637371
Received August 3, 2010; E-mail: teckpeng@ntu.edu.sg
demonstrated by the synthesis of 1,4-dicarbonyl compounds via
palladium-catalyzed coupling with acid chlorides.
In our attempts to develop the Umpolung chemistry of enone in
Abstract: The first water-tolerant, ketone-type indium homoeno-
late was synthesized via the oxidative addition of In/InCl3 to
enones. The reaction proceeds exclusively in aqueous media.
Both indium and indium(III) chloride are necessary for the smooth
conversion of the reaction. Similar results were obtained when
InCl or InCl2 was used in place of In/InCl3. The synthetic utility of
the indium homoenolate was demonstrated through the synthesis
of 1,4-dicarbonyl compounds via palladium-catalyzed coupling of
water, we studied the reaction of ethyl vinyl ketone with aldehyde
10
using our previously developed system of In/CuI/InCl3 in THF/
H2O. In addition to obtaining the ꢀ,γ-unsaturated ketone product,11,12
we also isolated a relatively polar byproduct by silica gel column
chromatography. NMR spectroscopy showed that the oil byproduct
was only a saturated derivative of ethyl vinyl ketone (four sets of
indium homoenolate with acid chloride.
1
peaks between 0-5 ppm in H NMR) and has an abnormal CH2
1
located at 0.83 ppm (t, J ) 7.16 Hz) in the H NMR and at 8.4
ppm in the 13C NMR (see the Supporting Information for details).
Homoenolate,1 a species containing an anionic carbon ꢀ to a
We hypothesized that it might be an organoindium complex, and
carbonyl group, is a potentially very useful three-carbon synthon
for organic synthesis. Therefore, there has been increasing interest
in the preparation and application of metal homoenolates in organic
synthesis.2-4 However, the use of metal homoenolates in organic
synthesis has not been fully explored, probably due to the limited
methods available for the facile generation of metal homoenolates.
Among the several methods developed for the synthesis of metal
homoenolate,2-4 the most commonly used method is pioneered by
Kuwajima and Nakamura via ring-opening of siloxycyclopropane
with various metal halides.2 Later, Yoshida and co-workers reported
the synthesis of zinc homoenolates via oxidative addition of zinc
to ꢀ-iodoesters.3 It is worthwhile to note that recent advances in
the generation of homoenolates directly from enals by nucleophilic
heterocyclic carbene (NHC) catalysis also provides a facile entry
to a homoenolate intermediate.5
Though research into the development of different metal ho-
moenolates (especially those of titanium and zinc homoenolates)
has been studied to a certain extent, to the best of our knowledge,
exploration on the synthesis of indium homoenolate has not been
undertaken so far. Furthermore, previous research on metal ho-
moenolates is mainly focused on carbonyl compounds of ester and
amide rather than ketone, which might be due to the fact that a
metal homoenolate (particularly titanium homoenolate) is so reactive
that it spontaneously reacts with the ketone to generate the more
stable cyclopropanol tautomer. In this regard, organoindium reagents
exhibit better compatibility with functional groups such as ketone,
aldehyde, and alcohol.6,7 Therefore, it is still desirable to develop
an efficient method for the synthesis of an indium homoenolate
containing a carbonyl group (especially ketone) which is currently
unavailable. Herein, we describe an efficient method for the
synthesis of a water-tolerant, ketone-type indium homoenolate via
oxidative addition of indium(I) reagent to enone in aqueous
media.8,9 The synthetic utility of the indium homoenolate was
this information encouraged us to look further into the byproduct.
In order to determine the structure, we were able to obtain a crystal
of the organoindium complex suitable for X-ray diffraction analysis
when phenyl vinyl ketone was used as a substrate and subjected to
an analogous reaction system as above (In/InCl3, CH3CN/H2O).
X-ray diffraction analysis proved that the product is a phenyl
substituted indium homoenolate, having a monomeric structure with
chelation of the two carbonyl groups to indium (Figure 1). The
coordination conformation of the central metal can be described
as a distorted trigonal bipyramid, in which C(9), C(18), and Cl(1)
are considered to occupy the equatorial plane and O(1) and O(2)
occupy the apical positions. The average CdO bond length of 1.232
Å is in accordance with that in titanium homoenolate (1.235 Å)2j
but is smaller than the CsO bond length in the enal-derived
allylnickel complex.9a The average CsC bond lengths (1.529 Å)
which are adjacent to the InsC bonds is slightly larger than those
in the titanium analogue (1.503 Å).2j
Figure 1. X-ray crystal structure of phenyl substituted indium homoenolate
(CCDC 776440). Selected bond lengths (Å) and angles (deg): In(1)-C(9)
2.141(6), In(1)-C(18) 2.174(6), In(1)-O(1) 2.431(7), In(1)-O(2) 2.413(5),
O(1)-C(7) 1.236(6), O(2)-C(16) 1.227(5), C(8)-C(9) 1.525(5), C(17)-C(18)
1.532(6);C(9)-In(1)-O(1)78.1(2),C(18)-In(1)-O(2)75.1(2),O(2)-In(1)-O(1)
168.7(3).
It is interesting to note that the indium homoenolate can be
generated in aqueous media. In other words, the indium homoeno-
† These authors contributed equally.
9
15852 J. AM. CHEM. SOC. 2010, 132, 15852–15855
10.1021/ja106925f  2010 American Chemical Society

C O M M U N I C A T I O N S
Table 1. Optimization of Reaction Conditionsa
Table 2. Substrate Scope Studiesa
entry
conditions
yield (%)b
1
2
3
4
5
6
In (0.8 equiv)/InCl3 (0.4 equiv), CH3CN/H2O
In (1.2 equiv), CH3CN/H2O
InCl3 (1.2 equiv), CH3CN/H2O
InCl (1.2 equiv), CH3CN/H2O
InCl2 (2.4 equiv), CH3CN/H2O
82 (90)c
0
0
81
78
56
In (0.8 equiv)/InCl3 (0.4 equiv), MeOH
a The reactions were carried out at room temperature for 24 h using
ethyl vinyl ketone (2 mmol, 1 equiv). b Isolated yield. c On a 20 mmol
scale.
late is tolerant to water, and currently there are only a few reports
related to the finding of water-tolerant organoindium complexes
(mainly allylic indium species).13 It was found that the indium
homoenolate is not sensitive to acid too. Though it decomposes
very slowly at room temperature, it can be stored at -80 °C without
decomposition.
Preliminary studies were carried out to optimize the yield of the
indium homoenolate using ethyl vinyl ketone as a substrate, and
the results are summarized in Table 1. As shown in Table 1, the
indium complex could be isolated in 82% yield when the reaction
was performed in CH3CN/H2O for 24 h using 0.8 equiv of indium
and 0.4 equiv of indium(III) chloride (entry 1).14 It is important to
note that both indium and indium(III) chloride are necessary for
the efficient transformation of the enone to the corresponding indium
homoenolate. Without either indium or indium(III) chloride, the
reaction did not occur (Table 1, entries 2 and 3). Considering that
0.8 equiv of indium and 0.4 equiv of indium(III) chloride are
equivalent to 1.2 equiv of indium(I) chloride (2In + InCl3 T 3InCl),
we hypothesized that the real indium species which effects the
transformation might be an indium(I) chloride. When performing
the above reaction using InCl as a reaction mediator, we were
pleased to observe that the reaction also took place in the presence
of InCl (1.2 equiv) or InCl2 (2.4 equiv), affording the desired
products in good yields of 81% and 78%, respectively (Table 1,
entries 4 and 5, and also refer to the Supporting Information for
the two equations which account for the theoretical amount of InClx
which should be used in the reaction).
Based on the fact that the R-position of the enone should be
protonated by H2O to generate the final indium homoenolate, it
was easy to rationalize the need of water. Screening of the reaction
in other organic solvents further revealed that water is indispensable
for the efficient progress of the reaction. No reaction occurred in
pure organic solvents such as THF, CH2Cl2, EtOAc, and CH3CN.
It is worthwhile to note that a moderate yield was obtained when
the same reaction was carried out in MeOH because it also can
serve as a proton source for protonation of the indium homoenolate
anion (Table 1, entry 6).
a The reactions were carried out at rt for 24 h using indium (1.6
mmol), indium(III) chloride (0.8 mmol), and enone (2 mmol) in
CH3CN/H2O (5 mL/5 mL). b Isolated yield.
yields (Table 2, entries 5-9). Notably, an enone with a methyl
group incorporated at the R-position also worked well under this
condition to give the product in good yield (Table 2, entry 10).
Unfortunately, no product was obtained when ꢀ-substituted enone
or R,ꢀ-unsaturated ester was used as the substrate (Table 2, entries
11-12).
The synthetic utility of the indium homoenolate was demon-
strated by subjecting it to acid chloride in the presence of a
palladium catalyst to afford 1,4-dicarbonyl compounds (Table
3).15-17 As shown in Table 3, in all cases, the coupling reactions
proceeded efficiently in the presence of PdCl2(PPh3)2 in THF to
afford the desired products in moderate to good yields. Aromatic
acid chlorides with electron-withdrawing or electron-donating
groups reacted well. Acid chlorides with a heteroaromatic substitu-
ent also could be effectively transformed (Table 3, entries 8-9).
In addition, aliphatic acid chlorides also worked well under the
optimized conditions, though moderate yields were obtained (Table
With the optimized reaction conditions in hand, a variety of
enones were used as substrates to investigate the general applicabil-
ity of the method for the preparation of indium homoenolates. As
shown in Table 2, in most cases, moderate to good yields of the
desired products were obtained. Aromatic enones with either
electron-withdrawing or electron-donating groups reacted well under
the optimized conditions (Table 2, entries 1-3). Enone with a
heteroaromatic substituent also could be effectively converted (Table
2, entry 4). Aliphatic enones also served as reactive substrates for
the reactions, affording the desired products in moderate to good
9
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C O M M U N I C A T I O N S
Table 3. Palladium-Catalyzed Coupling of Indium Homoenolates
Narasaka (Nanyang Technological University, NTU), Prof. Sunggak
Kim (NTU), Dr. Shunsuke Chiba (NTU) for helpful discussions,
and Dr. Yong-Xin Li (NTU) for X-ray support.
with Various Acid Chloridesa
Supporting Information Available: Experiment procedures, char-
1
acterization data of products, copies of H and 13C NMR spectra, and
CIF files. This material is available free of charge via the Internet at
http://pubs.acs.org.
entry
R1
R2
R3
product
yield (%)b
References
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
Et
H
4-NO2C6H4
4-BrC6H4
4-ClC6H4
Ph
4-MeC6H4
4-OMeC6H4
2-naphthyl
2-thienyl
2-furyl
2a
2b
2c
2d
2e
2f
2g
2h
2i
84
61c
84
83
87
74
89
90
98
69
64
78
70
86
85
79
84
98
70
85
(1) For reviews concerning homoenolate chemistry, see: (a) Werstiuk, N. H.
Tetrahedron 1983, 39, 205. (b) Hoppe, D.; Hense, T. Angew. Chem., Int.
Ed. Engl. 1997, 36, 2282. (c) Hoppe, D.; Marr, F.; Bruggemann, M. Top.
Organomet. Chem. 2003, 5, 61. (d) Kuwajima, I.; Nakamura, E. In
ComprehensiVe Organic Synthesis; Trost, B. M., Fleming, I., Eds.;
Pergamon: New York, 1991; Vol. 2, p 441 and references cited therein. (e)
Kuwajima, I.; Nakamura, E. In Topics in Current Chemistry; Springer:
Berlin, 1990; Vol. 155, p 3.
(2) (a) Nakamura, E.; Kuwajima, I. J. Am. Chem. Soc. 1977, 99, 7360. (b)
Nakamura, E.; Kuwajima, I. J. Am. Chem. Soc. 1984, 106, 3368. (c)
Nakamura, E.; Shimada, J.-i.; Kuwajima, I. Organometallics 1985, 4, 641.
(d) Oshino, H.; Nakamura, E.; Kuwajima, I. J. Org. Chem. 1985, 50, 2802.
(e) Nakamura, E.; Oshino, H.; Kuwajima, I. J. Am. Chem. Soc. 1986, 108,
3745. (f) Nakamura, E.; Aoki, S.; Sekiya, K.; Oshino, H.; Kuwajima, I.
J. Am. Chem. Soc. 1987, 109, 8056. (g) Nakamura, E.; Kuwajima, I. J. Am.
Chem. Soc. 1985, 107, 2138. (h) Horiguehi, Y.; Nakamura, E.; Kuwajima,
I. J. Org. Chem. 1986, 51, 4323. (i) Nakamura, E.; Kuwajima, I. J. Am.
Chem. Soc. 1983, 105, 651. For the X-ray analysis of a titanium
homoenolate, see: (j) Cozzi, P. G.; Carofiglio, T.; Floriani, C. Organome-
tallics 1993, 12, 2845.
(3) (a) Tamaru, Y.; Ochiai, H.; Nakamura, T.; Yoshida, Z. Angew. Chem., Int.
Ed. Engl. 1987, 26, 1157. (b) Tamaru, Y.; Ochiai, H.; Nakamura, T.;
Yoshida, Z. Tetrahedron Lett. 1986, 27, 955. (c) Tamaru, Y.; Ochiai, H.;
Nakamura, T.; Tsubaki, K.; Yoshida, Z. Tetrahedron Lett. 1985, 26, 5559.
(d) Ochiai, H.; Tamaru, Y.; Tsubaki, K.; Yoshida, Z. J. Org. Chem. 1987,
52, 4418.
(4) For other selected typical methods for the synthesis of metal homoenolate
by Knochel et al., see: (a) Sidduri, A.; Rozema, M. J.; Knochel, P. J. Org.
Chem. 1993, 58, 2694. (b) Still, W. C. J. Am. Chem. Soc. 1978, 100, 1481.
(c) Goswami, R. J. Org. Chem. 1985, 50, 5907.
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
PhCH2CH2
PhCH2
2j
2k
2l
4-ClC6H4
Ph
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
4-MeC6H4
2m
2n
2o
2p
2q
2r
2s
2t
4-MeC6H4
2-thienyl
PhCH2
PhCH2CH2
n-pentyl
c-hexyl
Ph
a The reactions were carried out at reflux for 24 h using indium
homoenolate (0.3 mmol), acid chloride (0.5 mmol), and PdCl2(PPh3)2
(0.025 mmol) in THF (3 mL). b Isolated yield based on acid chloride as
limiting reagent. c With ∼5% impurity which cannot be purified.
(5) For reviews regarding the generation of a homoenolate intermediate with
the use of NHC catalysis, see: (a) Nair, V.; Vellalath, S.; Babu, B. P. Chem.
Soc. ReV. 2008, 37, 2691. For recent examples, see: (b) Sohn, S. S.; Rosen,
E. L.; Bode, J. W. J. Am. Chem. Soc. 2004, 126, 14370. (c) Burstein, C.;
Glorius, F. Angew. Chem., Int. Ed. 2004, 43, 6205. (d) He, M.; Bode, J. W.
Org. Lett. 2005, 7, 3131. (e) Nair, V.; Vellalath, S.; Poonoth, M.; Mohan,
R.; Suresh, E. Org. Lett. 2006, 8, 507. (f) Nair, V.; Poonoth, M.; Vellalath,
S.; Suresh, E.; Thirumalai, R. J. Org. Chem. 2006, 71, 8964. (g) Nair, V.;
Vellalath, S.; Poonoth, M.; Suresh, E. J. Am. Chem. Soc. 2006, 128, 8736.
(h) Phillips, E. M.; Wadamoto, M.; Chan, A.; Scheidt, K. A. Angew. Chem.,
Int. Ed. 2007, 46, 3107. (i) Chiang, P.-C.; Kaeobamrung, J.; Bode, J. W.
J. Am. Chem. Soc. 2007, 129, 3520. (j) Wadamoto, M.; Phillips, E. M.;
Reynolds, T. E.; Scheidt, K. A. J. Am. Chem. Soc. 2007, 129, 10098. (k)
He, M.; Bode, J. W. J. Am. Chem. Soc. 2008, 130, 418. (l) Nair, V.; Babu,
B. P.; Vellalath, S.; Suresh, E. Chem. Commun. 2008, 747. (m) Chan, A.;
Scheidt, K. A. J. Am. Chem. Soc. 2007, 129, 5334. (n) Phillips, E. M.;
Reynolds, T. E.; Scheidt, K. A. J. Am. Chem. Soc. 2008, 130, 2416. (o)
Chan, A.; Scheidt, K. A. J. Am. Chem. Soc. 2008, 130, 2740. (p) Seayad,
J.; Patra, P. K.; Zhang, Y.; Ying, J. Y. Org. Lett. 2008, 10, 953. (q) Sohn,
S. S.; Bode, J. W. Org. Lett. 2005, 7, 3873. (r) He, M.; Struble, J. R.;
Bode, J. W. J. Am. Chem. Soc. 2006, 128, 8418.
3, entries 10-11). Moreover, the reactions of various indium
homoenolates with 4-methylbenzoyl chloride proceeded efficiently
to give the final products in good yields (Table 3, entries 12-20).
Finally, it is important to note that both of the two R groups attached
to the indium (R2InCl) can be efficiently transferred in the
palladium-catalyzed coupling with acid chloride.
In summary, a novel method for the synthesis of the first indium
homoenolate was achieved via the oxidative addition of InCl (or
In/InCl3) to enones in aqueous media. The indium homoenolate
was found to be water-tolerant and represents one of the few already
discovered organoindium complexes. The structure of one of the
indium homoenolates has been confirmed by single crystal X-ray
analysis. The method also provides an easy access to the synthesis
of a carbonyl-containing organoindium reagent and ketone-type
homoenolate which are not readily available by conventional
methods. The synthetic utility of the indium homoenolate was
demonstrated through the synthesis of 1,4-dicarbonyl compounds
via palladium-catalyzed coupling with acid chloride. It is important
to note that 1,4-dicarbonyl compounds are important intermediates
in organic synthesis which are difficult to construct using conven-
tional methods.15 The transformation of the enone to indium
homoenolate also represents one of the few Umpolung chemistries
of enone with inversion of its ꢀ-carbon polarity. Further studies
concerning other methods for the synthesis of indium homoenolates
and their synthetic utility in organic synthesis are currently in
progress.
(6) Takami, K.; Yorimitsu, H.; Shinokubo, H.; Matsubara, S.; Oshima, K. Org.
Lett. 2001, 3, 1997.
(7) For the recent development of aryl and benzyl indium reagents which were
pioneered by Knochel et al., see: (a) Chen, Y. H.; Knochel, P. Angew.
Chem., Int. Ed. 2008, 47, 7648. (b) Chen, Y. H.; Sun, M.; Knochel, P.
Angew. Chem., Int. Ed. 2009, 48, 2236. (c) Papoian, V.; Minehan, T. J.
Org. Chem. 2008, 73, 7376. (d) Chupak, L. S.; Wolkowski, J. P.; Chantigny,
Y. A. J. Org. Chem. 2009, 74, 1388. (e) Fujiwara, N.; Yamamoto, Y. J.
Org. Chem. 1999, 64, 4095.
(8) Organic reactions in water; for reviews, see: (a) Li, C. J.; Chan, T. H.
Tetrahedron 1999, 55, 11149. (b) Li, C. J. Chem. ReV. 2005, 105, 3095.
(c) Li, C. J. Chem. ReV. 1993, 93, 2023. (d) Li, C. J.; Chen, L. Chem. Soc.
ReV. 2006, 35, 68. (e) Dallinger, D.; Kappe, C. O. Chem. ReV. 2007, 107,
2563. (f) Kobayashi, S.; Manabe, A. K. Acc. Chem. Res. 2002, 35, 209.
(g) Lindstrom, U. M. Chem. ReV. 2002, 102, 2751. (h) Li, C. J. Acc. Chem.
Res. 2002, 35, 533. (i) Li, C. J. Green Chem. 2002, 4, 1. (j) Miyabe, H.;
Naito, T. Org. Biomol. Chem. 2004, 2, 1267. (k) Herrer´ıas, C. I.; Yao,
X. Q.; Li, Z. P.; Li, C. J. Chem. ReV. 2007, 107, 2546. (l) Chauhan, K. K.;
Frost, C. G. J. Chem. Soc., Perkin Trans. 1 2000, 3015. (m) Babu, G.;
Perumal, P. T. Aldrichimica Acta 2000, 33, 16.
Acknowledgment. We gratefully acknowledge the Nanyang
Technological University, Ministry of Education Research Fund
Tier 2 (No. M45110000), and A*STAR SERC Grant (No.
0721010024) for the funding of this research. We also thank Prof.
Chi Wi Ong (National Sun Yat Sen University), Prof. Koichi
(9) For the formation of nickel-π-allyl complexes via oxidative addition of
nickel(0) to enones in the presence of Lewis acids, see: (a) Johnson, J. R.;
Tully, P. S.; Mackenzie, P. B.; Sabat, M. J. Am. Chem. Soc. 1991, 113,
6172. (b) Grisso, B. A.; Johnson, J. R.; Mackenzie, P. B. J. Am. Chem.
Soc. 1992, 114, 5160.
9
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C O M M U N I C A T I O N S
(10) For our previous works on the development of Barbier-Grignard-type
alkylation reaction of imine, aldehyde, nitrone, and R,ꢀ-unsaturated carbonyl
compounds in aqueous media using In/CuI via a radical type mechanism,
see: (a) Shen, Z. L.; Loh, T. P. Org. Lett. 2007, 9, 5413. (b) Shen, Z. L.;
Cheong, H. L.; Loh, T. P. Chem.sEur. J. 2008, 14, 1875. (c) Shen, Z. L.;
Yeo, Y. L.; Loh, T. P. J. Org. Chem. 2008, 73, 3922. (d) Yang, Y. S.;
Shen, Z. L.; Loh, T. P. Org. Lett. 2009, 11, 1209. (e) Shen, Z. L.; Cheong,
H. L.; Loh, T. P. Tetrahedron Lett. 2009, 50, 1051. For a review of our
previous works on indium, see: (f) Loh, T. P.; Chua, G. L. Chem. Commun.
2006, 2739.
(17) For pioneering works relating to the use of triorganoindium reagent (R3In,
prepared via transmetalation of RLi or RMgX with InCl3) in palladium-
catalyzed coupling reactions by Sarandeses et al., see: (a) Pe´rez, I.; Sestelo,
J. P.; Sarandeses, L. A. J. Am. Chem. Soc. 2001, 123, 4155. (b) Pe´rez, I.;
Sestelo, J. P.; Sarandeses, L. A. Org. Lett. 1999, 1, 1267. For selected
other examples concerning palladium-catalyzed coupling of R3In or other
types of organoindium reagents with various electrophiles (such as ArX,
acid chloride, benzyl halides, alkenyl halides), see: (c) Caeiro, J.; Sestelo,
J. P.; Sarandeses, L. A. Chem.sEur. J. 2008, 14, 741. (d) Pena, M. A.;
Pe´rez, I.; Sestelo, J. P.; Sarandeses, L. A. Chem. Commun. 2002, 2246. (e)
Nomura, R.; Miyazaki, S.-I.; Matsuda, H. J. Am. Chem. Soc. 1992, 114,
2738. (f) Lee, P. H.; Sung, S.; Lee, K. Org. Lett. 2001, 3, 3201. (g) Pena,
M. A.; Sestelo, J. P.; Sarandeses, L. A. Synthesis 2003, 780. (h) Gotov,
B.; Kaufmann, J.; Schumann, H.; Schmalz, H. G. Synlett 2002, 361. (i)
Jaber, N.; Gelman, D.; Schumann, H.; Dechert, S.; Blum, J. Eur. J. Org.
Chem. 2002, 1628. (j) Lee, K.; Lee, J.; Lee, P. H. J. Org. Chem. 2002, 67,
8265. (k) Lee, K.; Seomoon, D.; Lee, P. H. Angew. Chem., Int. Ed. 2002,
41, 3901. (l) Takami, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2002, 4,
2993. (m) Lee, P. H.; Lee, S. W.; Lee, K. Org. Lett. 2003, 5, 1103. (n)
Takami, K.; Mikami, S.; Yorimitsu, H.; Shinokubo, H.; Oshima, K. J. Org.
Chem. 2003, 68, 6627. (o) Lee, P. H.; Lee, S. W.; Seomoon, D. Org. Lett.
2003, 5, 4963. (p) Pena, M. A.; Sestelo, J. P.; Sarandeses, L. A. Synthesis
2005, 485. (q) Pena, M. A.; Sestelo, J. P.; Sarandeses, L. A. J. Org. Chem.
2007, 72, 1271. (r) Font-Sanchis, E.; Ce´spedes-Guirao, F. J.; Sastre-Santos,
Á.; Ferna´ndez-La´zaro, F. J. Org. Chem. 2007, 72, 3589. (s) Riveiros, R.;
Saya, L.; Sestelo, J. P.; Sarandeses, L. A. Eur. J. Org. Chem. 2008, 1959.
(11) Similar results regarding the synthesis of ꢀ,γ-unsaturated ketone has already
been reported by Kim and co-workers: Kang, S.; Jang, T. S.; Keum, G.;
Kang, S. B.; Han, S. Y.; Kim, Y. Org. Lett. 2000, 2, 3615.
(12) For a recent report for the formation of a 1,2-diol via a Zn/InCl3-mediated
cross-coupling reaction of enone with aldehyde in THF/H2O by our group,
see: Yang, Y. S.; Shen, Z. L.; Loh, T. P. Org. Lett. 2009, 11, 2213.
(13) For selected examples of organoindium complexes, see: (a) Yasuda, M.;
Haga, M.; Baba, A. Organometallics 2009, 28, 1998. (b) Yasuda, M.;
Kiyokawa, K.; Osaki, K.; Baba, A. Organometallics 2009, 28, 132. (c)
Nishimoto, Y.; Moritoh, R.; Yasuda, M.; Baba, A. Angew. Chem., Int. Ed.
2009, 48, 4577.
(14) Performing the same reaction in CH3CN/D2O (1:1) also produced the
R-deuterated indium homoenolate in a similar yield of 81%.
(15) DeMartino, M. P.; Chen, K.; Baran, P. S. J. Am. Chem. Soc. 2008, 130,
11546, and references cited therein.
(16) See the Supporting Information for details of the optimization of reaction
conditions for palladium-catalyzed coupling of indium homoenolate with
acid chloride using various organic solvents and palladium catalysts.
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