Preparation of dicationic chalcogenolate-bridged diruthenium complexes and their dual catalytic activity toward reactions between propargylic alcohols and acetone

Organometallics

Volumn 24, Issue 24, 2005, Pages 5799-5801

  Onodera, Gen ^a   Matsumoto, Hideyuki ^a   Nishibayashi, Yoshiaki ^b   Uemura, Sakae ^a  

^a KYOTO UNIVERSITY   (Japan)

^b UNIVERSITY OF TOKYO   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONE; ALCOHOLS; CATALYST ACTIVITY; CATALYSTS; REACTION KINETICS; RUTHENIUM COMPOUNDS;

DIRUTHENIUM COMPLEXES; PROPARGYLIC ALCOHOLS;

COMPLEXATION;

EID: 28944434611     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om050831j     Document Type: Review

References (28)

1. (a) The thiolate-bridged diruthenium complexes were found to provide a unique bimetallic reaction site for activation and transformation of various terminal alkynes; see: Nishibayashi, Y.; Yamanashi, M.; Wakiji, I.; Hidai, M. Angew. Chem., Int. Ed. 2000, 39, 2909 and references therein.
2. (b) The methanethiolate-bridged diruthenium complexes are commercially available from Wako Pure Chemical Industries (Japan) as met-DIRUX (methanethiolate-bridged diruthenium complet; 1a, 130-14581) and met-DIRUX-OTf (2a, 132-14781).
3. For the preparation of neutral chalcogenolate-bridged diruthenium complexes and their catalytic activities toward propargylic substitution reactions, see: (a) Nishibayashi, Y.; Imajima, H.; Onodera, G.; Hidai, M.; Uemura, S. Organometallics 2004, 23, 26.
4. (b) Nishibayashi, Y.; Imajima, H.; Onodera, G.; Inada, Y.; Hidai, M.; Uemura, S. Organometallics 2004, 23, 5100.
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20. (3E,5E)-6-Phenylhexa-3,5-diene-2-one (5a) was identified by comparing its spectroscopic data with those in the literature; Mitsudo, T.; Takagi, M.; Zhang, S.-W.; Watanabe, Y. J. Organomet. Chem. 1992, 423, 405.
21. The formation of some polymers, which might be derived from 4 and products, is one reason for the low yield of both 5 and 6.
22. This type of isomerization reaction is known as the Meyer-Schuster and Rupe rearrangements: (a) Meyer, K. H.; Schuster, K. Chem. Ber. 1922, 55, 819.
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24. For a review, see: (c) Swaminathan, S.; Narayanan, K. V. Chem. Rev. 1971, 71, 429 and references therein.
25. α carbon of an allenylidene ligand has been reported: Esteruelas, M. A.; Gómez, A. V.; Lahoz, F. J.; López, A. M.; Oñate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
26. The ruthenium-catalyzed isomerization of propargylic alcohols into the corresponding α,β-unsaturaed aldehydes was reported: Cadirno, V.; Díez, J.; García-Garrido, S. E.; Gimeno, J. Chem. Commun. 2004, 2716.
27. Wakatsuki and co-workers proposed that allenylidene complexes were reactive intermediates in the isomerization of propargylic alcohols into the corresponding α,β-unsaturated aldehydes catalyzed by some ruthenium complexes: Suzuki, T.; Tokunaga, M.; Wakatsuki, Y. Tetrahedron Lett. 2002, 43, 7531.
28. γ atom of the allenylidene ligand on dinuclear ruthenium complexes to give the corresponding propargylic substituted products such as propargylic ethers in high yields with complete selectivity.