Preparation, Properties, and Reactions of Metal-Containing Heterocycles, XCII. Steric and Solvent Effects of the Different Reaction Patterns of Activated Alkynes with Diphosphamanganacyclopropanes

✍ Scribed by Lindner, Ekkehard ;Fisahn, Paul ;Fawzi, Riad ;Steimann, Manfred

• Publisher: Wiley (John Wiley & Sons)
• Year: 1996
• Tongue: English
• Weight: 933 KB
• Volume: 129
• Category: Article
• ISSN: 0009-2940
• DOI: 10.1002/cber.19961290212

✦ Synopsis

Bicyclic manganese compounds / P-P bonds / Activated alkynes The product pattern of the reaction of the alkynes ZCECZ (4-11) [Z = C02R: R = Me (4), Et (5), nPr (6), iPr (7), nBu (8), nPent (91, neo-Pent (lo), cyc-Hex (ll)] with the diphosphamanganacyclopropanes ( O C ) 4 M F P w 2 R 2 (1 -3) depends on the polarity of the employed solvent. Whereas in n-hexane the diphosphamanganabicyclo[3.3.0]octadienones 12a-q, the diphosphamanganacyclopentenes 13a-h, and the triphosphamanganabicyclo[3.2.0]heptenones 14a-h are formed, m THF only the five-membered heterocycles 13 occur. Compound 14d is easily oxidized to the corresponding oxide 15d. According to X-ray structural analyses, both 14d