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Innovative reactions mediated by zirconocene
Author(s) -
Fujita Kazuya,
Yorimitsu Hideki,
Oshima Koichiro
Publication year - 2004
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.20004
Subject(s) - chemistry , alkene , hydride , alkoxide , medicinal chemistry , stereoselectivity , tributyltin hydride , organic chemistry , reagent , aldehyde , catalysis , metal
Radical reactions mediated by Schwartz reagent and zirconocene(alkene) complex are firstly described. Schwartz reagent is a promising alternative to tributyltin hydride and the first transition metal hydrido complex used as a radical mediator in organic synthesis. A zirconocene(alkene) complex effects single electron transfer to alkyl halide to generate the corresponding alkyl radical. Secondly, serendipitous allylic CH bond activation of the coordinating alkene of zirconocene(alkene) complex and its application to organic synthesis are summarized. By utilizing equilibrium between zirconocene(alkene) and zirconocene 2‐alkenyl hydride, reaction of acid chloride with zirconocene(alkene) provides the corresponding homoallylic alcohol by sequential attacks of the hydride and 2‐alkenyl moieties. A set of hydride and 2‐alkenyl attacks on 1,4‐diketone yields 6‐heptene‐1,4‐diol derivative in high yield with high stereoselectivity. Selective capture of the hydride with diisopropyl ketone gives zirconocene 2‐alkenyl alkoxide, which is a useful reagent for stereoselective allylation of aldehyde and imine. α‐Halo carbonyl compounds undergo radical allylation with the zirconocene 2‐alkenyl alkoxide which serves as a substitute for allyltin. © 2004 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 4: 110–119; 2004: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20004