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Chemistry of Ru(& 6 ‐1,3,5‐cyclooctatriene)(η 2 ‐dimethyl fumarate) 2
Author(s) -
Mitsudo TakeAki,
Ura Yasuyuki,
Kondo Teruyuki
Publication year - 2006
Publication title -
the chemical record
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.61
H-Index - 78
eISSN - 1528-0691
pISSN - 1527-8999
DOI - 10.1002/tcr.20076
Subject(s) - hydroamination , chemistry , norbornadiene , intramolecular force , cyclohexene , reactivity (psychology) , catalysis , medicinal chemistry , cycloaddition , stereochemistry , organic chemistry , medicine , alternative medicine , pathology
The chemistry of a novel zerovalent Ru complex, Ru(η 6 ‐cot)(η 2 ‐dmfm) 2 ( 1 ) (cot=1,3,5‐cyclooctatriene; dmfm=dimethyl fumarate), is reviewed with a focus on its reactivity toward phosphines, amines, and H 2 O, as well as arenes and p ‐quinones. A variety of novel zerovalent Ru complexes were synthesized from Ru(η 6 ‐cot)(η 2 ‐dmfm) 2 ( 1 ), and it was shown that the complexes preferably bear both electron‐donating and ‐accepting ligands simultaneously to exhibit thermodynamic stability. The first isolable zerovalent Ru aqua complexes were successfully prepared, and in these complexes, the generation of a chiral center on the O atom of the coordinated H 2 O was disclosed. In addition, the characteristic catalytic activity of 1 in organic synthesis was considered by reviewing recently developed novel reactions: (i) dimerization of 2,5‐norbornadiene to pentacyclo[6.6.0.0 2,6 .0 3,13 .0 10,14 ]tetradeca‐4,11‐diene (PCTD), (ii) intramolecular hydroamination of aminoalkynes to cyclic imines, (iii) formal [4+2] cycloaddition of alkynes with dmfm to trans ‐4‐cyclohexene‐1,2‐dicarboxylates, and (iv) co‐dimerization of dihydrofurans with α,β‐unsaturated esters to 2‐alkylidenetetrahydrofurans. The products obtained here are expected to be used as novel functional organic monomers. © 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 6: 107–116; 2006: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20076