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DOI: 10.1002/cctc.

201100185
Ligand-Consuming Formation of Rhodium-Hydride Species from
[Rh(OH)(cod)]2 Without any Additional Hydride Sources for Catalytic Olefin
Isomerizations and Cyclobutene Synthesis
Ken Motokura, Kohei Nakayama, Akimitsu Miyaji, and Toshihide Baba*[a]

General methods for the formation of metal hydrides (M H) re-


quire an additional hydride source (Scheme 1 a). To realize the
formation of a metal hydride without additives, we investigat-

Scheme 1. a) Metal-hydride formation with a hydride source, and b) ligand-


consuming generation of a metal-hydride.

ed the ligand-consuming formation of the metal hydride, as Scheme 2. Generation of Rh H species from [Rh(OH)(cod)]2.
shown in Scheme 1 b. If hydride abstraction from a ligand
occurs at the metal center, the structure of the ligand molecule
coordinating to the metal should changes. The distorted proceeds, oxidized COD [cyclooctenone (1 a) and cyclooctadie-
ligand can then be expected to be easily eliminated from the nol (1 b)] and a coordinatively unsaturated Rh H species
metal center. This ligand-consuming methodology should should form.[6] Herein, we report a novel phenomenon for the
enable the formation of not only metal hydrides, but also gen- generation of Rh H species from [Rh(OH)(cod)]2 for catalytic
erate a coordinatively unsaturated environment at the metal reactions.
center, which would be expected to be catalytically active. cis/trans-Isomerization of Z-stilbene is a well-known metal-
The cyclooctadienerhodium hydroxide dimer {[Rh(OH)- hydride catalyzed reaction. This isomerization was examined
(cod)]2} (COD = 1,5-cyclooctadiene) is a well known homogene- using several rhodium complexes (Table 1).[7] [Rh(OH)(cod)]2
ous catalyst. Although various organic transformations using showed a high catalytic performance, however, the reaction
[Rh(OH)(cod)]2 have been reported,[1,2] its reactivity is limited to barely proceeded using [RhCl(cod)]2 and [Rh(cod)2]BF4. Follow-
the transmetallation between the Rh OH and R X (X = B, Si, H ing the reaction using [Rh(OH)(cod)]2, 1 a and 1 b were detect-
(activated), etc.) groups or the Rh alkoxide formation from the ed in the reaction mixture. The total amount of 1 a, 1 b, and
R OH group. Discovery of novel reaction pathways and cataly- their isomers was 12 mmol.[8] Migration of terminal olefins
ses for [Rh(OH)(cod)]2 have thus received considerable using [Rh(OH)(cod)]2 was also examined (Table 2). Allylben-
attention. zenes with electron-donating groups were effectively trans-
Mimoun and coworkers reported a Wacker-type oxidation of
C=C bonds via a Rh OH intermediate, affording ketones and
Rh H.[3,4] The stoichiometric oxidation of the COD-ligand of Table 1. cis/trans-Isomerization of Z-Stilbene.[a]
[(N3-ligand)-RhI(cod)]+ with H2O2 was also reported.[3,5] These re-
sults encouraged us to investigate the ligand-consuming for-
mation of Rh H species from [Rh(OH)(cod)]2 through oxidation
of its COD ligand by the OH group (Scheme 2). If this reaction
Catalyst Conversion [%] Yield [%]
[a] Dr. K. Motokura, K. Nakayama, Dr. A. Miyaji, Prof. T. Baba [Rh(OH)(cod)]2 98 88
Department of Environmental Chemistry and Engineering [RhCl(cod)]2 5 2
Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku [Rh(cod)2]BF4 7 3
Yokohama, 226-8502 (Japan) none 10 2
E-mail: tbaba@chemenv.titech.ac.jp
[a] Reaction conditions: Z-stilbene (1.0 mmol), catalyst (Rh: 82 mmol), 1,4-
Supporting Information for this article is available on the WWW under
dioxane (2 mL), 100 8C, Ar, 24 h.
http://dx.doi.org/10.1002/cctc.201100185.

ChemCatChem 2011, 3, 1419 1421  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1419
Table 2. Double Bond Migration of Terminal Olefins.[a]

Entry Substrate Conversion [%] Yield [%] E:Z Scheme 4. Migration of deuterium induced by treatment of a-deuterated
styrene with [Rh(OH)(cod)]2.
1 R=H 88 85 93:7
2 R = p-CH3-Ph 92 89 88:12
3 R = p-OMe-Ph 93 92 87:13

4 R= > 99 99 93:7

5 R = SiMe3 78 78 92:7

[a] Reaction conditions: olefin (1.0 mmol), catalyst (rhodium: 82 mmol),


1,4-dioxane (2 mL), 100 8C, Ar, 1 h.

Scheme 5. Migration of p-methyl(allyl)benzene in 1,4-[D8]dioxane.

ferred to conjugated products with approximately 90 % E-se-


lectivity, which was accompanied by the formation of 1 a and
1 b.[9,10]
To confirm the formation of Rh H species under the catalyt-
ic reaction conditions, hydride transfer reactions using deuter-
ated styrenes were performed. The reaction between
[D8]styrene (> 98 atom % D) and allylbenzene afforded deuter-
ated 1-propenylbenzene (Scheme 3). The amount of deuterium
in the styrene double bond decreased to approximately 63
83 %. Incorporation of deuterium into the terminal methyl
group of 1-propenylbenzene indicates that the insertion of the
allylbenzene double bond into the Rh H (Rh D) species oc-
curred during olefin migration. In addition, the treatment of a-
deuterated styrene (> 98 atom % D) with [Rh(OH)(cod)]2 in-
duced migration of deuterium (Scheme 4). These results clearly Figure 1. High field 1H NMR spectrum of [Rh(OH)(cod)]2 in 1,4-[D8]dioxane.
indicate in situ formation of a Rh H species. To confirm the hy- Rh H: (d = 1.20 ppm, doublet, J103Rh H = 44.1 Hz).
dride source, migration of p-methyl(allyl)benzene was exam-
ined in 1,4-[D8]dioxane. Incorporation of deuterium into the
migration product did not occur (Scheme 5). This result indi- 10 3) than that of the [Rh(OH)(cod)]2 signal appearing at d =
cates that the dioxane solvent did not act as a hydride source. 1.53.5 ppm (see the Supporting Information). Almost all of
Consequently, the olefin isomerizations were catalyzed by the the [Rh(OH)(cod)]2 complex is stable, and the amount of the
Rh H species generated in situ from Rh OH and its COD Rh H species is significantly lower than that of [Rh(OH)(cod)]2
ligand. under 1H NMR analysis conditions. Conversely, after isomeriza-
The high field 1H NMR spectrum of a solution of [Rh(OH)- tion of Z-stilbene, 12 mmol of oxidized COD (1) forms from
(cod)]2 in 1,4-[D8]dioxane is shown in Figure 1. The resonance 41 mmol of [Rh(OH)(cod)]2. These results indicate that approxi-
centered at d = 1.20 ppm with a 103Rh H coupling of 44.1 Hz mately 15 % of [Rh(OH)(cod)]2 is converted into the Rh H spe-
indicates the formation of a Rh H species.[11] This signal ap- cies during the catalytic reaction.
pears at a lower field compared to other reported metal-hy- Recently, MizorokiHeck-type coupling reactions between al-
dride complexes (d = 5 to 40 ppm) with electron-donating kynes and electron-deficient olefins were reported for Pd H
ligands such as PPh3.[11,12] This result suggests a coordinatively and Ru H catalysts.[13] To extend the catalytic application of
unsaturated environment of the in situ generated Rh H spe- the in situ generated Rh H species, the coupling reaction of
cies. The integration of this signal is considerably smaller ( diphenylacetylene and methyl acrylate (2) was examined using
[Rh(OH)(cod)]2. Contrary to ex-
pectation, an 81 % yield of 1,2-
diphenyl-3-methoxycarbonylcy-
clobutene (3) was obtained as
the main product, accompanied
by a 12 % yield of the Mizoroki
Heck-type eneyne coupling
products (4), as shown in
Scheme 3. Reaction between [D8]styrene and allylbenzene. Table 3, entry 1. These products

1420 www.chemcatchem.org  2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemCatChem 2011, 3, 1419 1421
Chem. Soc. 2005, 127, 15354; e) T. Nishimura, T. Katoh, T. Hatashi,
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[5] a) B. de Bruin, M. J. Boerakker, J. J. J. M. Donners, B. E. C. Christiaans,
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of 2 [%] of 3 [%] 2E, 4Z 2E, 4E de Bruin, J. A. Brands, J. J. J. M. Donners, M. P. J. Donners, R. de Gelder,
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1 [Rh(OH)(cod)]2 OMe > 99 81 10 2
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2 [RhCl(cod)]2 OMe 25 2 <1 trace
2004, 23, 4236; d) A. Dauth, J. A. Love, Chem. Rev. 2011, 111, 2010; e) C.
3 [Rh(cod)2]BF4 OMe 9 7 trace trace
Tejel, M. P. del Ro, J. A. Lpez, M. A. Ciriano, Chem. Eur. J. 2010, 16,
4 none OMe <1 trace trace trace
11261.
5 [Rh(OH)(cod)]2 O nBu > 99 83 7 2
[6] Closed-shell allylic C H activation of COD and a radical chain electron
6 [Rh(OH)(cod)]2 NH tBu > 99 65 17 10
transfer oxidation of COD involving disproportionation of small
[a] Reaction conditions: diphenylacetylene (1.0 mmol), 2 (0.33 mmol), cat- amounts of rhodium(II) intermediates have been reported, see: a) M.
alyst (rhodium: 82 mmol), 1,4-dioxane (2 mL), 80 8C, Ar, 24 h. Yields and Martn, E. Sola, O. Torres, P. Plou, L. A. Oro, Organometallics 2003, 22,
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technique. c) D. G. H. Hetterscheid, M. Klop, R. J. N. A. M. Kicken, J. M. M. Smits, E. J.
Reijerse, B. de Bruin, Chem. Eur. J. 2007, 13, 3386; d) D. G. H. Hettersc-
heid, B. de Bruin, J. M. M. Smits, A. W. Gal, Organometallics 2003, 22,
3022. In this study, the RhI species with a hydroxide ligand acts as a cat-
were barely detected when using [RhCl(cod)]2 and [Rh- alyst precursor; however, the formation of oxidized COD and the rhodi-
um hydride species from above mentioned pathways cannot be com-
(cod)2]BF4 rather than [Rh(OH)(cod)]2. Other electron-deficient pletely ruled out.
olefins, such as acrylamide derivatives, are also suitable for the [7] D. Gauthier, A. T. Lindhardt, E. P. K. Olsen, J. Overgaard, T. Skydstrup, J.
cyclobutene synthesis in the presence of [Rh(OH)(cod)]2. Am. Chem. Soc. 2010, 132, 7998.
This is the first report of a cyclobutene synthesis from al- [8] The ketone/alcohol ratio was 1.8/1.0.
[9] To exclude the possibility of a base-catalyzed migration mechanism
kynes and electron-deficient olefins.[14] The mechanism for the (Ref. 9), the reaction of p-methyl(allyl)benzene in the presence of D2O
cyclobutene formation has not yet been clarified. Two plausi- was performed. MS and 1H NMR analysis revealed no incorporation of
ble pathways include a metallacyclopentene intermediate or deuterium into the migration product (see the Supporting Information).
hydrometallation of the alkyne (see the Supporting Informa- [10] a) T. Baba, Catal. Surv. Jpn. 2000, 4, 17; b) D. Kishore, S. Kannan, Green
Chem. 2002, 4, 607.
tion). The coordinatively unsaturated environment of the Rh H [11] A Rh H complex with a 103Rh H coupling of 43.2 Hz was reported, see:
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