Rh-catalyzed carbonylation of arylzinc compounds yielding symmetrical diaryl ketones by the assistance of oxidizing agents

Article abstract of DOI:10.1021/jo1025173

Carbonylative homocoupling of arylzinc compounds 1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was achieved in the presence of Rh-dppf catalyst, affording symmetrical diaryl ketones in good yields. Under similar conditions, Pd or Ni catalysts induced oxidative homocoupling of 1 to yield biaryls instead. The beneficial catalysis by Rh in the carbonylation was presumed to stem from the facility by which the migration of the aryl ligand to CO at the Rh³⁺ intermediate occurred.

Full text of DOI:10.1021/jo1025173

NOTE
pubs.acs.org/joc
Rh-Catalyzed Carbonylation of Arylzinc Compounds Yielding
Symmetrical Diaryl Ketones by the Assistance of Oxidizing Agents
Kana Kobayashi,† Yugo Nishimura,† Fuxing Gao,‡ Kazuma Gotoh,† Yasushi Nishihara,† and Kentaro Takagi*,†
†Department of Chemistry, Faculty of Science, Okayama University, Tsushima, Okayama 700-8530, Japan
‡Department of Chemistry, Xinyang Normal University, Xinyang, Henan 464000, China
S Supporting Information
b
ABSTRACT: Carbonylative homocoupling of arylzinc compounds
1 using 1 atm of CO and 1,2-dibromoethane as an oxidant was
achieved in the presence of Rh-dppf catalyst, affording symmetrical
diaryl ketones in good yields. Under similar conditions, Pd or Ni
catalysts induced oxidative homocoupling of 1 to yield biaryls instead.
The beneficial catalysis by Rh in the carbonylation was presumed to
stem from the facility by which the migration of the aryl ligand to CO at the Rh3þ intermediate occurred.
Scheme 1. Synthesis of Ketones Utilizing Catalytic Carbo-
nylative Couplings
arbon monoxide serves as a versatile and straightforward
building block to construct the CO segment in ketones
C
through catalytic cross-coupling between organometallic nucleo-
philes R-m and carbon electrophiles R0-X, accompanied by the
insertion of carbon monoxide (Scheme 1).1 This carbonylative
cross-coupling is valuable in organic syntheses since it not only
retains the beneficial properties of cross-coupling, e.g., high
efficiency and high chemoselectivity of the catalytic process,
but also eliminates the need for carboxylic acid derivatives R0CO-
X as carbon electrophiles, thus readily providing efficient access
to polyfunctionalized ketones.1,2 For the synthesis of symme-
trical ketones, carbonylative homocouplings, available with single
coupling components, e.g., R-m in oxidative reactions or R0-X in
reductive reactions, should provide convenient alternatives for
the carbonylative cross-coupling (Scheme 1). To our knowledge,
the protocols used previously to achieve efficient catalytic reac-
tions with various combinations of R-m with oxidizing agents1a,3
or R0-X with reducing agents1a,4 have been severely limited. In
the course of our study on the synthesis and applications of
arylzinc compounds ArZnX 1,5 we attempted the unprecedented
catalytic carbonylation of 1 with the assistance of an oxidizing
agent, with the intention of developing efficient and novel access
to symmetrical diaryl ketones. Diaryl ketones are a prevailing
structural motif in various fields including medicinal and phar-
maceutical chemistry,6 functional molecules,7 and advanced
materials8 and are useful in molecular transformations as syn-
thetic intermediates.9
product, biphenyl 4a, was obtained in high yield (entries 1-4). For-
tunately, the Rh catalyst successfully achieved the concomitant
insertion of CO, affording benzophenone 3a in high yield (entry
5). Co catalyst also afforded 3a, together with 4a (entry 8).10 For
the Rh catalyst, 1,10-bis(diphenylphosphino)ferrocene dppf was
the best ligand among those examined (entries 5-7). As
oxidants, O2, CuCl2, Cu(OAc)2, and ClCH2CH2Cl were less
effective than 2 (entries 9-12). Even when the amounts of Rh-
dppf catalyst and oxidant 2 were decreased to 2 mol % and 1.2
equiv, respectively, the yield of reaction product 3a remained
high (entries 13 and 14). Other arylmetallic compounds Ar-m
(m = B, Sn, or Mg) were less effective than 1a under the
examined conditions (entries 15-17). As shown in Table 2,
ArZnX 1 containing such functional groups as cyano (entry 2),
alkoxycarbonyl (entry 3), bromo (entries 4 and 5), alkoxy (entry
6), or alkyl (entries 7 and 8) at ortho (entry 5), meta (entry 8), or
para (entries 2-4, 6, and 7) positions took part in the desired
reaction equally well. This Rh-catalyzed reaction is also applic-
able to a 2-thienylzinc compound (entry 9). Thus, by means of 1
and 2, this is the first instance in which a Rh-dppf catalyst
achieved carbonylative homocoupling of arylmetallic nucleo-
philes Ar-m by the assistance of oxidizing agents.3a,3b In contrast
The reaction of phenylzinc iodide 1a with CO (1 atm) was
examined in THF at 60 oC for 3 h in the presence of 10 mol % of
catalyst and oxidizing agent (2 equiv). As shown in Table 1,
utilizing 1,2-dibromoethane 2 as the oxidant, the reaction of 1a
took place smoothly under CO atmosphere by catalysis with Pd,
Ni, or Rh to consume 1a nearly quantitatively (entries 1-6).
However, in runs using Pd or Ni catalysts, the reaction mainly
took place between 1a and 2, and the oxidative homocoupling
Received: December 20, 2010
Published: February 10, 2011
r
2011 American Chemical Society
1949
dx.doi.org/10.1021/jo1025173 J. Org. Chem. 2011, 76, 1949–1952
|

The Journal of Organic Chemistry
NOTE
Table 1. Catalytic, Oxidative Homocoupling of 1a under CO
Atmospherea
Scheme 2. Symmetrical Diaryl Ketones from Aryl Halides
yield (%)b
entry
catalyst
oxidant
3a
4a
1
PdCl2(PPh3)2
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
O2
15
33
<5
6
80
2
PdCl2(dppf)
3
NiCl2(PPh3)2
9
76
9
Scheme 3. Effect of CO on the Reaction between 1a and 2
4
NiCl2(dppf)
5
RhCl(PPh3)3
71
95
44
30
11
11
7
6
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppp
CoCl2/3PPh3
<5
36
36
65
<5
11
<5
<5
<5
<5
<5
11
7
8
9
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
1/2[RhCl(cod)]2/dppf
10
11
12
13c
14d
15e
16f
17g
CuCl2
Cu(OAc)2
ClCH2CH2Cl
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
BrCH2CH2Br
15
87
82
5
11
20
a 1a (0.4 mmol), oxidant (0.8 mmol), catalyst (0.04 mmol), CO (1 atm),
and THF (0.45 mL) were used for all entries, except for entry 9 (1 atm
oxidant) and entries 14-17 (0.02 mmol catalyst). b GLC yield. The
c
cross-coupling with ArX (Scheme 2).1 Therefore, the present
reaction provides the most convenient and efficient route to
symmetrical diaryl ketones from aryl halides.16
amount of catalyst was reduced to 0.008 mmol. d The amount of oxidant
was reduced to 0.48 mmol. e PhB(OH)2 and CsF (0.4 mmol) were used
f
g
in place of 1a. Ph4Sn was used in place of 1a. PhMgBr was used in
place of 1a.
A detailed mechanism remains to be clarified. However, any
mechanism must take into account the reason for the superiority
of Rh as a catalyst compared to Pd or Ni, in view of the well-
known efficiency of the latter in similar carbonylative cross-
coupling to yield ketones,1,11-14,17 as well as oxidative homo-
coupling to yield biaryls.18 The catalytic activity of several
complexes was examined in the reaction of 1a with 2 under N2
in stead of CO atmosphere (Scheme 3). In every run, undertaken
at room temperature for 1 h, 4a was obtained in high yield (1-1-
1-5), revealing that all metals examined (Pd, Ni, and Rh19)
exhibited excellent catalytic activity toward oxidative homocou-
pling using 1 and 2 as the reaction components. This result is
rather surprising, because, in previous runs, Pd or Ni catalysts
required much harsher condition (60 °C, for 3 h) to go to com-
pletion (Table 1). In fact, under the usual CO atmosphere,
oxidative homocoupling proceeded far more slowly at room
temperature (2-1 and 2-2). With the Rh catalyst, CO caused an
enormous decrease in catalytic activity toward oxidative homo-
coupling, and while CO insertion occurred primarily, it was quite
slow (2-3). Thus, the activity of all catalysts toward oxidative
homocoupling was decreased by CO, presumably due to coor-
dination to the metal center. This view might be supported by the
inferiority of carbonyl catalysts, Ni(CO)2(PPh3)2 or RhCl(CO)-
(PPh3)2, in oxidative homocoupling (1-6 and 1-720).
Table 2. Rh-Catalyzed Synthesis of Symmetrical Ketonesa
entry
RZnI
product
yieldb (%)
1
2
3
4
5
6
7
8
9
1a (R = C6H5)
3a
3b
3c
3d
3e
3f
79
93
74
84
88
95
78
91
97
1b (R = p-NCC6H4)
1c (R = p-EtO2CC6H4)
1d (R = p-BrC6H4)
1e (R = o-BrC6H4)
1f(R = p-MeOC6H4)
1g (R = p-MeC6H4)
1h (R = m-MeC6H4)
1i (R = 2-C4H3S)
3g
3h
3i
a RZnI (0.8 mmol), BrCH2CH2Br (1.6 mmol), catalyst (0.04 mmol),
CO (1 atm), and THF (0.9 mL) were used for all entries. b Isolated yield.
to Ar-m where m = Sn,11 B,12 Si,13 or In,14 1 (m = Zn) is the only
Ar-m to be available for direct reaction between aryl halides and
metallic species,5,15 while it is not available for carbonylative
A plausible reaction path of carbonylative, oxidative homo-
coupling is depicted in Scheme 4, where two transmetalations
(reaction a), migratory insertion (reaction b), reductive elimination
1950
dx.doi.org/10.1021/jo1025173 |J. Org. Chem. 2011, 76, 1949–1952

The Journal of Organic Chemistry
NOTE
Scheme 4. Reaction Path
(22.2 mg, 0.04 mmol), and THF (0.10 mL) was purged with CO after
being connected with a balloon filled with CO. The solution was stirred
for 10 min at ambient temperature before 0.73 mL of 1.1 mol/L THF
solution of 4-cyanophenylzinc iodide 1b (0.80 mmol) and 1,2-dibro-
moethane 2 (0.066 mL, 0.80 mmol) were added successively and stirred
at 60 °C for 3 h. After the successive treatment of the resulting mixture
with aqueous HCl and brine, the ether extract was chromatographed on
a silica gel column, affording 86.3 mg of 4,40-dicyanobenzophenone 3b
(93%): white solid; mp 157-159 °C (lit.22 mp 159.5-160 °C); 1H NMR
(300 MHz, CDCl3) δ 7.83 (d, 4H, J = 8.7 Hz), 7.88 (d, 4H, J = 8.7 Hz);
13C NMR (75.7 MHz, CDCl3) δ 116.5, 117.7, 130.2, 132.4, 139.7, 193.4.
’ ASSOCIATED CONTENT
S
Supporting Information. General method, compound
b
characterization data, and copies of the 1H and 13C NMR spectra.
This material is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Scheme 5. Migratory Insertion vs. Reductive Elimination at
Intermediate B
Corresponding Author
*E-mail: takagi@cc.okayama-u.ac.jp.
’ ACKNOWLEDGMENT
This work was supported by a Grant-in-Aid for Scientific
Research (No. 20550043) from the Japan Society for the
Promotion of Science.
’ REFERENCES
(1) (a) Brunet, J.-J.; Chauvin, R. Chem. Soc. Rev. 1995, 89–95. (b)
Brennfuehrer, A.; Neumann, H.; Beller, M. Angew. Chem., Int. Ed. 2009,
48, 4114–4133.
(2) (a) Mori, M. Synthesis of Natural Products via Palladium-
Catalyzed Carbonylation. In Handbook of Organopalladium Chemistry
for Organic Synthesis; Negishi, E., Ed.; Wiley-Interscience: New York,
2002; Vol. II, pp 2663-2682. (b) Couladouros, E. A.; Mihou, A. P.;
Bouzas, E. A. Org. Lett. 2004, 6, 977–980. (c) Gao, S.; Wang, Q.; Chen,
C. J. Am. Chem. Soc. 2009, 131, 1410–1412.
(3) For Pd-catalyzed carbonylation of ArHgCl or Ar4Sn with CuX2
as oxidizing agent, yielding symmetrical diaryl ketones in low to
moderate yields, see: (a) Heck, R. F. J. Am. Chem. Soc. 1968, 90,
5546–5548. (b) Ohe, T.; Motofusa, S.; Ohe, K.; Uemura, S. Bull. Chem.
Soc. Jpn. 2001, 74, 1343–1348. For Pd-catalyzed carbonylation of
alkylzinc iodide with allyl benzoate or O2 as oxidizing agent, see:(c)
Yasui, K.; Fugami, K.; Tanaka, S.; Tamaru, Y. J. Org. Chem. 1995, 60,
1365–1380. (d) Jackson, R. F. W.; Turner, D.; Block, M. H. J. Chem. Soc.,
Perkin Trans. 1 1997, 865–870.
(reaction c), and oxidation of the reduced catalyst (M = Rh(I), Pd0,
or Ni0) to a higher oxidation state (reaction d) are involved.3b-3d In
addition, coordination of CO may take place at any one of the inter-
mediates, A, C, or D, preceding the migratory insertion to form
acylcomplex C (Z = Ar or Br). As a side reaction, biaryl for-
mation probably takes place through reaction a, followed by
another reductive elimination (reaction c0) and then reaction
d, where CO acts as a spectator ligand but affects the activity of
the catalyst to yield 4 (Scheme 5). Under slightly forcing
conditions (60 °C), Rh catalyst first achieves the formation of
3, implying that the migratory insertion b takes place selec-
tively and rapidly at the key intermediate B, followed by
reductive elimination c to form 3. This pathway overcomes
reductive elimination c0 to form 4 from B with Z = Ar.21 In
contrast, Pd or Ni catalysts make the migratory insertion b less
facile than Rh does,21 and even under CO atmosphere, these
catalysts afforded 4 predominantly, via B with Z = Ar, although
slight heating is required to induce the reaction.
(4) For Pd-catalyzed carbonylation of Ar2Iþ with Zn or In as
reducing agent, yielding symmetrical diaryl ketones, see: (a) Uchiyama,
M.; Suzuki, T.; Yamazaki, Y. Chem. Lett. 1983, 1201–1202. (b) Zhou, T.;
Chen, Z.-C. Synth. Commun. 2002, 32, 3431–3435. For [HFe(CO)4]--
catalyzed carbonylation of iodobenzene, yielding benzophenone, see:
(c) Brunet, J.-J.; Zaizi, A. E. J. Organomet. Chem. 1995, 486, 275–277.
For Co2(CO)8-mediated carbonylation of iodoarenes, yielding symme-
trical diaryl ketones, see:(d) Enquist, P.-A.; Nilsson, P.; Larhed, M. Org.
Lett. 2003, 5, 4875–4878.
(5) (a) Ejiri, S.; Odo, S.; Takahashi, H.; Nishimura, Y.; Gotoh, K.;
Nishihara, Y.; Takagi, K. Org. Lett. 2010, 12, 1692–1695. (b)
Takahashi, H.; Inagaki, S.; Yoshii, N.; Gao, F.; Nishihara, Y.; Takagi,
K. J. Org. Chem. 2009, 74, 2794–2797. (c) Kawamoto, T.; Ejiri, S.;
Kobayashi, K.; Odo, S.; Nishihara, Y.; Takagi, K. J. Org. Chem. 2008,
73, 1601–1604. (d) Takahashi, H.; Hossain, K. M.; Nishihara, Y.;
Shibata, T.; Takagi, K. J. Org. Chem. 2006, 71, 671–675. (e) Ikegami,
R.; Koresawa, A.; Shibata, T.; Takagi, K. J. Org. Chem. 2003, 68,
2195–2199.
In conclusion, the synthesis of functionalized symmetrical biaryl
ketones from readily available arylzinc nucleophiles and CO (1 atm)
revealed that only Rh exhibited excellent catalytic activity for the
carbonylation. Rh also suppressed the homocoupling of arylzinc
compounds with 1,2-dibromoethane as oxidant, which takes place
extremely easily, not only by catalysis with Rh but also with Pd or Ni
under milder conditions in the absence of CO.
’ EXPERIMENTAL SECTION
Representative Procedure. The reaction flask containing the
solution composed of [RhCl(cod)]2 (9.8 mg, 0.02 mmol), dppf
1951
dx.doi.org/10.1021/jo1025173 |J. Org. Chem. 2011, 76, 1949–1952

The Journal of Organic Chemistry
NOTE
(6) For recent example, see: (a) Luque-Ortega, J. R.; Reuther, P.;
Rivas, L.; Dardonville, C. J. Med. Chem. 2010, 53, 1788–1798. (b)
Vooturi, S. K.; Cheung, C. M.; Rybak, M. J.; Firestine, S. M. J. Med. Chem.
2009, 52, 5020–5031. (c) Plazuk, D.; Vessieres, A.; Hillard, E. A.; Buriez,
O.; Labbe, E.; Pigeon, P.; Plamont, M.-A.; Amatore, C.; Zakrzewski, J.;
Jaouen, G. J. Med. Chem. 2009, 52, 4964–4967.
(7) For recent example, see: (a) Qin, Q.; Mague, J. T.; Pascal, R. A.,
Jr. Org. Lett. 2010, 12, 928–930. (b) Kim, H.; So, S. M.; Yen, C. P.-H.;
Vinhato, E.; Lough, A. J.; Hong, J.-I.; Kim, H.-J.; Chin, J. Angew. Chem.,
Int. Ed. 2008, 47, 8657–8660. (c) Fukuda, M.; Sekiya, R.; Kuroda, R.
Angew. Chem., Int. Ed. 2008, 47, 706–710. (d) Yang, H.-B.; Ghosh, K.;
Zhao, Y.; Northrop, B. H.; Lyndon, M. M.; Muddiman, D. C.; White,
H. S.; Stang, P. J. J. Am. Chem. Soc. 2008, 130, 839–841. (e) Ruhland, K.;
Obenhuber, A.; Hoffmann, S. D. Organometallics 2008, 27, 3482–3495.
(f) Dewal, M. B.; Xu, Y.; Yang, J.; Mohammed, F.; Smith, M. D.; Shimizu,
L. S. Chem. Commun. 2008, 3909–3911.
(8) For recent example, see: (a) Kizilkaya, C.; Karatas, S.; Apohan,
N.-K.; Guengoer, A. J. Appl. Polym. Sci. 2010, 115, 3256–3264. (b)
Tanaka, D.; Nakagawa, K.; Higuchi, M.; Horike, S.; Kubota, Y.;
Kobayashi, T. C.; Takata, M.; Kitagawa, S. Angew. Chem., Int. Ed.
2008, 47, 3914–3918. (c) Peng, H. J. Am. Chem. Soc. 2008, 130, 42–
43. (d) Wang, D.; Zhang, S.; Zhang, Y.; Wang, H.; Mu, J.; Wang, G.;
Jiang, Z. Dyes Pigments 2008, 79, 217–223.
(9) For recent example, see:(a) Albrecht, K.; Yamamoto, K. J. Am.
Chem. Soc. 2009, 131, 2244–2251. (b) Claramunt, R. M.; Lopez, C.;
Perez-Medina, C.; Perez-Torralba, M.; Elguero, J.; Escames, G.; Acuna-
Castroviejo, D. Bioorg. Med. Chem. 2009, 17, 6180–6187. (c) Navale,
T. S.; Zhai, L.; Lindeman, S. V.; Rathore, R. Chem. Commun. 2009,
2857–2859. (d) Tantama, M.; Lin, W.-C.; Licht, S. J. Am. Chem. Soc.
2008, 130, 15766–15767. (e) Lam, O. P.; Anthon, C.; Heinemann,
F. W.; O’Connor, J. M.; Meyer, K. J. Am. Chem. Soc. 2008, 130, 6567–
6576. (f) Hagberg, D. P.; Yum, J.-H.; Lee, H.-J.; De Angelis, F.;
Marinado, T.; Karlsson, K. M.; Humphry-Baker, R.; Sun, L.; Hagfeldt,
A.; Graetzel, M.; Nazeeruddin, M. K. J. Am. Chem. Soc. 2008, 130, 6259–
6266. (g) Papageorgiou, G.; Ogden, D.; Corrie, J. E. T. Photochem.
Photobiol. Sci. 2008, 7, 423–432. (h) Liu, L.; Zhang, G.; Xiang, J.; Zhang,
D.; Zhu, D. Org. Lett. 2008, 10, 4581–4584. (i) Dumur, F.; Mayer, C. R.;
Dumas, E.; Miomandre, F.; Frigoli, M; Secheresse, F. Org. Lett. 2008, 10,
321–324. (j) Seo, J. W.; Kim, H. J.; Lee, B. S.; Katzenellenbogen, J. A.;
Chi, D. Y. J. Org. Chem. 2008, 73, 715–718.
availability3a3b16a-16e of starting materials in comparison with m = Zn,
and the low to moderate yields of products reported,3a3b16b,16d,16e our
method is far more useful.(a) Larock, R. C.; Hershberger, S. A. J. Org.
Chem. 1980, 45, 3840–3846. (b) Cho, C. S.; Yoshimori, Y.; Uemura, S.
Bull. Chem. Soc. Jpn. 1995, 68, 950–957. (c) Kang, S.-K.; Ryu, H.-C.;
Choi, S.-C. Synth. Commun. 2001, 31, 1035–1039. (d) Ohe, T.; Ohe, K.;
Uemura, S.; Sugita, N. J. Organomet. Chem. 1988, 344, C5–C7. (e) Cho,
C. S.; Ohe, T.; Uemura, S. J. Organomet. Chem. 1995, 496, 221–226.
(17) (a) Negishi, E.; Zhang, Y.; Shimoyama, I.; Wu, G. J. Am. Chem.
Soc. 1989, 111, 8018–8020. (b) Negishi, E.; Makabe, H.; Shimoyama, I.;
Wu, G.; Zhang, Y. Tetrahedron 1998, 54, 1095–1106. (c) Wang, Q.;
Chen, C. Tetrahedron Lett. 2008, 49, 2916–2921.
(18) (a) Hassan, J.; Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M.
Chem. Rev. 2002, 102, 1359–1470. (b) Hossain, K. M.; Kameyama, T.;
Shibata, T.; Takagi, K. Bull. Chem. Soc. Jpn. 2001, 74, 2415–2420. (c) Jin,
L.; Zhang, H.; Li; Sowa, J. R.; Lei, A. J. Am. Chem. Soc. 2009, 131, 9892–
9893. (d) Jin, L.; Xin, J.; Huang, Z.; He, J.; Lei, A. J. Am. Chem. Soc. 2010,
132, 9607–9609.
(19) Under conditions similar to those of runs 1-5, functionalized
1, e.g., 1c or 1f, took part in the reaction to yield the corresponding
biaryls in 82% or 97% yields, respectively. Recently, Rh-catalyzed
oxidative homocoupling of arylmetallic nucleophiles was reported for
the first time, using arylboronic acids and 2,2,6,6-tetramethylpiperidine-
N-oxyl radical as the nucleophile and oxidant, respectively. See: Vogler,
T.; Studer, A. Adv. Synth. Catal. 2008, 350, 1963–1967.
(20) In the reaction solution of runs 1-7, 3a was not detected.
(21) At present, it is not clear which property of the catalyst is most
critical for facilitating the migratory insertion in the reported reaction. In
general, the rate is supposed to tend to increase as the positive charge on
the carbonyl carbon increases. See, for example: Crabtree, R. H. The
Organometallic Chemistry of the Transition Metals, 5th ed.; Wiley-Inter-
science: New York, 2009; p 182. DFT calculations on model compounds
showed that the value becomes highest with the Rh3þ intermediate:
(CH3)3Rh(CO), 0.596; (CH3)2Pd(CO), 0.543; (CH3)2Ni(CO),
0.543; CH3Rh(CO); 0.382.
(22) Humphreys, R. W. R.; Arnold, D. R. Can. J. Chem. 1977, 55,
2286–2291.
(10) For Co-mediated carbonylative homocoupling of arylzinc
compounds yielding symmetrical diaryl ketones, see: Devasagayaraj,
A.; Knochel, P. Tetrahedron Lett. 1995, 36, 8411–8414.
(11) (a) Andersson, Y.; Laagstroem, B. J. Chem. Soc., Perkin Trans. 1
1995, 287–289. (b) Moriello, A. S.; Balas, L.; Ligresti, A.; Cascio, M. G.;
Durand, T.; Morera, E.; Ortar, G.; Di Marzo, V. J. Med. Chem. 2006, 49,
2320–2332. (c) Cai, M.; Zheng, G.; Ding, G. Green Chem. 2009, 11,
1687–1693.
(12) (a) Ishiyama, T.; Kizaki, H.; Miyaura, N.; Suzuki, A. Tetrahe-
dron Lett. 1993, 34, 7595–8. (b) Ishiyama, T.; Kizaki, H.; Hayashi, T.;
Suzuki, A.; Miyaura, N. J. Org. Chem. 1998, 63, 4726–4731. (c) Dai, M.;
Liang, B.; Wang, C.; You, Z.; Xiang, J.; Dong, G.; Chen, J.; Yang, Z. Adv.
Synth. Catal. 2004, 346, 1669–1673. (d) Neumann, H.; Brennfuehrer,
A.; Beller, M. Chem.—Eur. J. 2008, 3645–3652. (e) O’Keefe, B. M.;
Simmons, N.; Martin, S. F. Org. Lett. 2008, 10, 5301–5304. (f) Tambade,
P. J.; Patil, Y. P.; Panda, A. G.; Bhanage, B. M. Eur. J. Org. Chem. 2009,
3022–3025.
(13) Hatanaka, Y.; Fukushima, S.; Hiyama, T. Tetrahedron 1992, 48,
2113–2126.
(14) Lee, S. W.; Lee, K.; Seomoon, D.; Kim, S.; Kim, H.; Kim, H.;
Shim, E.; Lee, M.; Lee, S.; Kim, M.; Lee, P. H. J. Org. Chem. 2004, 69,
4852–4855.
(15) Krasovskiy, A.; Malakhov, V.; Gavryushin, A.; Knochel, P.
Angew. Chem., Int. Ed. 2006, 45, 6040–6044.
(16) Another synthetic method of symmetrical diaryl ketones from
Ar-m (m = Hg,3a,16a Bi,16b Sn,3b Pb,16c or B16d,16e) and CO without
oxidants is known, where Ar-m oxidatively adds to catalysts. Compared
to the harshness of the conditions,3a,16a toxicity,3a,3b16a16c and/or
1952
dx.doi.org/10.1021/jo1025173 |J. Org. Chem. 2011, 76, 1949–1952