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Selective Hydrogenation of Avermectin Catalyzed by Iridium-Phosphine Complexes

✍ Scribed by Xiao-Yan MA; Kun WANG; Lei ZHANG; Xian-Jun LI; Rui-Xiang LI


Publisher
John Wiley and Sons
Year
2007
Tongue
English
Weight
74 KB
Volume
25
Category
Article
ISSN
0256-7660

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✦ Synopsis


Abstract

A series of new iridium complexes, IrCl(COD)(TMOPP) (1) [COD=1,5‐cyclooctadiene, TMOPP=tris(4‐ methoxyphenyl)phosphine], IrCl(COD)(TFMPP) (2) [TFMPP=tris(4‐trifluoromethylphenyl)phosphine], IrCl‐ (COD)(BDNA) (3) [BDNA=1,8‐bis(diphenylphosphinomethyl)naphthalene], IrCl(COD)(BISBI) (4) [BISBI=2,2′‐bis(diphenylphosphinomethyl)biphenyl] and IrCl(COD)(BDPB) (5) [BDPB=1,2‐bis(diphenylphosphinometh‐ yl)benzene], were synthesized and characterized by NMR spectra and elemental analyses. In order to obtain the relationships between complex structures and their catalytic properties, IrCl(COD)(DPPM) (6) [DPPM=bis(diphenylphosphino)methane], IrCl(COD)(DPPE) (7) [DPPE=1,2‐bis(diphenylphosphino)ethane], IrCl(COD)(DPPP) (8) [DPPP=1,3‐bis(diphenylphosphino)propane] and IrCl(COD)(TPP) (9) [TPP=triphenylphosphine], were also synthesized according to the reported methods. The hydrogenation results showed that the low electronic density at the central metal was favorable to increase the catalytic activity for the hydrogenation of avermectin, but decrease the selectivity to ivermectin. The complex with a large chelating ring and a bulky chelating backbone would easily cause the cleavage of CO bond in avermectin to give a byproduct avermectin aglycon.


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## Abstract Treatment of [Ir~2~(μ‐H)(μ‐Pz)~2~H~3~(NCMe)(P__i__Pr~3~)~2~] (1) with one equivalent of HBF~4~ or [PhNHCHPh]BF~4~ affords efficient catalysts for the homogeneous hydrogenation of __N__‐benzylideneaniline. The reaction of 1 with HBF~4~ leads to the trihydride–dihydrogen complex [Ir~2~(μ