178809-67-1Relevant academic research and scientific papers
Stereospecific syntheses of functionalised iron alkyl complexes with a stereogenic metal center from an iron formyl precursor
Guillevic, Marie Andree,Bregaint, Patrik,Lapinte, Claude
, p. 157 - 162 (1996)
Treatment of the stable formyl complex Fe(C5Ph5)(CO)(PMe3)CHO (1) with an excess of methyl triflate and subsequent addition of NH4PF6 produces the secondary carbene complex [Fe(η5-C5Ph5)(CO)(PMe3)(=CHOMe)][PF6] (2, 93%). Methyl lithium acts as a dealkylating reagent with 2 to regenerate 1 (81%). Treatment of methoxycarbene complex 2 with LiAlH4 gives the methoxymethyl complex Fe(η5-C5Ph5)(CO)(PMe3)(CH2OMe) (3) in 95% yield. Similarly, reaction of 2 with LiAlD4 gives a 90: 10 mixture of Fe(η5-C5Ph5)(CO)(PMe3)(CHDOMe) (3 d1, 80%) diastereoisomers. The carbene complex 2 reacts with MeONa to give the iron dimethylacetal complex Fe(η5-C5Ph5)(CO)(PMe3){CH(OMe)2} (4, 55%). The cyano(methoxy)methyl complex Fe(η5-C5Ph5)(CO)(PMe3){CH(CN)(OMe)} (5, 85%) is obtained from the reaction of 2 with 1 equivalent of KCN. NMR analyses of the crude product revealed that complex 5 was formed as a 85: 15 mixture of diastereoisomers. The carbene complex 2 reacts with TMSC≡CLi to afford a 90: 10 mixture of diastereoisomers of the stable methoxy(trimethylsilylethynyl)methyl iron complexes Fe(C5Ph5)(CO)(PMe3) {CH(OMe)(C≡CTMS)} (6). After extraction and filtration 6 is isolated as a pure diastereoisomer in 63% yield.
