The Nazarov cyclization of two types of pyrrole derivatives was effectively catalyzed by 5 mol% alumina-supported ironAwhich provided the desired cyclization with high trans selectivity in good to excellent yield. The cyclized product was next reacted with a vinyl ketone in the presence of the same iron salt to afford the corresponding Michael product. A sequential type Nazarov/Michael reaction of pyrrole derivatives has also been accomplished; the synthetic route to 4,5-dihydrocyclopenta[b]pyrrol-6A
Hexamethyldigermane, Me3GeGeMe3, reacted with various alkynes in the presence of platinum complexes at 120 °C to afford Z–1,2-bis(germyl)ethenes in moderate to good yields. Terminal alkynes exhibit higher reactivities than internal ones. [Pt(acac)2] and [Pt(dba)2] serve as efficient catalysts, while [Pt(PPh3)4], [PtCl2(PPh3)2], and [Pt(dba)2]-phosphite were found to be inactive. Four- and six-membered cyclic oligogermanes, such as dodecamethylcyclohexagermane, (Me2Ge)6, reacted with alkynes in the presence of platinum catalysts to yield 1,4-digermacyclohexa-2,5-dienes in ca. 30% yield. The reactions of phenylacetylene with 1,2-digermacyclohexa-3,5-dienes afforded the corresponding 1,4-digermacycloocta-2,5,7-trienes in 93% yield. Bis(germyl)platinum complexes having various tertiary phosphine ligands have been prepared as models of a key intermediate in the above mentioned catalytic bis-germylation of alkynes, and their structures have been established by spectroscopic methods and X-ray crystallography. Bis(germyl)platinum complexes reacted with phenylacetylene to give the corresponding insertion products, germyl(germylvinyl)platinum species, whose structures have been determined by spectroscopic and X-ray analysis. Germyl(germylvinyl)platinum complexes were found to liberate a bis-germylation product of the alkyne upon heating. The result supports a mechanism involving the oxidative addition of a digermane to a Pt(0) complex, the insertion of an alkyne into one of the two Pt-Ge bonds to give a germyl(germylvinyl)platinum species, and the reductive elimination of the bis-germylation product of the alkyne. Evidence suggesting the extrusion of a germylene unit from the bis-germylplatinum species has been obtained, accounting for the generation courses of other by-products.
A hybrid dendrimer with alternating Si and
Ge atoms in the chains has been synthesized by the
divergent growth method using
Me(PhMe2Ge)2SiLi as a
branching reagent. The structure of the first
generation
of the hybrid permethylated dendrimer 1G has
been
established by X-ray crystallography.
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