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DOI: 10.1002/cctc.

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
[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.

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-
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  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,
Table 3. Cyclobutene (3) synthesis from diphenylacetylene and electron- Angew. Chem. 2007, 119, 5025; Angew. Chem. Int. Ed. 2007, 46, 4937;
deficient olefins (2).[a] f) Z.-M. Sun, J. Zhang, J. R. S. Manan, P. Zhao, J. Am. Chem. Soc. 2010,
132, 6935.
[3] B. de Bruin, P. H. M. Budzelaar, A. W. Gal, Angew. Chem. 2004, 116, 4236;
Angew. Chem. Int. Ed. 2004, 43, 4142.
[4] H. Mimoun, M. M. P. Machirant, I. S. Roch, J. Am. Chem. Soc. 1978, 100,
[5] a) B. de Bruin, M. J. Boerakker, J. J. J. M. Donners, B. E. C. Christiaans,
P. P. J. Schlebos, R. de Gelder, J. M. M. Smits, A. L. Spek, A. W. Gal, Angew.
Entry Catalyst R Conversion Yield Yield of 4 [%] Chem. 1997, 109, 2153; Angew. Chem. Int. Ed. Engl. 1997, 36, 2064; b) B.
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,
J. M. M. Smits, A. W. Gal, A. L. Spek, Chem. Eur. J. 1999, 5, 2921;
1 [Rh(OH)(cod)]2 OMe > 99 81 10 2
c) D. G. H. Hetterscheid, J. M. M. Smits, B. de Bruin, Organometallics
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
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,
conversion was determined by using 1H NMR using internal standard 5406; b) B. de Bruin, D. G. H. Hetterscheid, Eur. J. Inorg. Chem. 2007, 211;
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:
species seems to be necessary for both reaction pathways.[14a] S. Sarkar, S. Li, B. B. Wayland, J. Am. Chem. Soc. 2010, 132, 13569.
In summary, we have discovered a novel catalytic behavior [12] I. del Rosal, L. Maron, R. Poteau, F. Jolibois, Dalton Trans. 2008, 3959.
of [Rh(OH)(cod)]2 involving the Rh H formation without addi- [13] a) A. T. Lindhardt (ne Hansen), M. L. H. Mantel, T. Skydstrup, Angew.
Chem. 2008, 120, 2708; Angew. Chem. Int. Ed. 2008, 47, 2668; b) N. M.
tion of an external hydride source. The in situ generated Rh H Neisius, B. Plietker, Angew. Chem. 2009, 121, 5863; Angew. Chem. Int. Ed.
species was catalytically active for olefin isomerizations and cy- 2009, 48, 5752.
clobutene synthesis from alkynes and electron-deficient ole- [14] Cyclobutene synthesis from alkynes and alkenes has been reported,
fins. see: a) T.-a. Mitsudo, Y. Hori, Y. Watanabe, J. Organomet. Chem. 1987,
334, 157; b) T.-a. Mitsudo, H. Naruse, T. Kondo, Y. Ozaki, Y. Watanabe,
Angew. Chem. 1994, 106, 595; Angew. Chem. Int. Ed. Engl. 1994, 33, 580;
Keywords: carbocycles homogeneous catalysis c) A. Tenaglia, L. Giordano, Synlett 2003, 2333; d) N. Riddell, W. Tam, J.
Org. Chem. 2006, 71, 1934; e) R. W. Jordan, K. Villeneuve, W. Tam, J. Org.
isomerization rhodium Chem. 2006, 71, 5830; f) A. Frstner, A. Schlecker, C. W. Lehmann, Chem.
Commun. 2007, 4277; g) J. Treutwein, G. Hilt, Angew. Chem. 2008, 120,
[1] K. Yoshida, T. Hayashi in Modern Rhodium-Catalyzed Organic Reactions 6916; Angew. Chem. Int. Ed. 2008, 47, 6811; h) T. Kondo, Synlett 2008,
(Ed.: P. A. Evans), Wiley-VCH, Weinheim, 2005, chap. 3. 629.
[2] a) T. Hayashi, K. Yamasaki, Chem. Rev. 2003, 103, 2829; b) Y. Nakao, J.
Chen, H. Imanaka, T. Hiyama, Y. Ichikawa, W.-L. Duan, R. Shintani, T. Hay-
ashi, J. Am. Chem. Soc. 2007, 129, 9137; c) T. Seiser, N. Cramer, J. Am. Received: June 3, 2011
Chem. Soc. 2010, 132, 5340; d) A. Funayama, T. Satoh, M. Miura, J. Am. Published online on July 15, 2011

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