期刊
MOLECULES
卷 15, 期 4, 页码 2631-2650出版社
MDPI
DOI: 10.3390/molecules15042631
关键词
iron; phosphoramidites; X-ray; chiral at metal; benzylic oxidations
资金
- National Science Foundation [CHE-0420497, CHE-9974801, CHE-9708640]
New phosphoramidite complexes of iron were synthesized and structurally characterized. Reaction of the known chiral phosphoramidites (RO)(2)PNR'(2) (R = binaphthyl, R' = CH3, 1a; R = binaphthyl, R' = benzyl, 1b) with [FeBr(Cp)(CO)(2)] afforded the title compounds [FeBr(Cp)(CO)(1a,b)] (4a, b) in 34 and 65 % isolated yields as mixtures of diastereomers, since both the metal and the ligand are stereogenic. Similarly, reaction of 1b with [Fe(Cp)I(CO)(2)] in the presence of catalytic [Fe(Cp)(CO)(2)](2) afforded [Fe(Cp)I(CO)(1b)] (5b) in 81% yield as a mixture of diastereomers. The molecular structures of 4a, 4b and 5 were determined, revealing a pseudo octahedral coordination geometry about the iron center. The new metal complexes are catalytically active in the oxidation of benzylic methylene groups to the corresponding ketones, utilizing t-BuOOH as oxidant 92 mol% catalyst, 36 h, room temperature, 31-80% yield).
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