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An Unusual Rearrangement during the Oxidative Addition of Hexafluoroacetone and Trifluoroacetophenone to 2-Bornanylen(dimethylphosphino)methyl Imine: Formation of a P=C Double Bond

✍ Scribed by Frank Borkenhagen; Ion Neda; Holger Thönnessen; Peter G. Jones; Reinhard Schmutzler


Publisher
John Wiley and Sons
Year
1998
Tongue
German
Weight
139 KB
Volume
624
Category
Article
ISSN
0372-7874

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✦ Synopsis


The reaction of aminomethyl dimethylphosphine oxide and (1 R)±(+)-camphor furnished the r 4 k 5 -P Schiff base 1. Reduction of 1 with trichlorosilane, followed by alkaline hydrolysis, led to 2-bornanylen(dimethylphosphino)methyl imine 2. The 1,2-r 5 k 5 oxaphosphetane 5, formed in the reaction of 2 with hexafluoroacetone, spontaneously rearranged into the P=C doubly bonded compound 9 at room temperature. Likewise, by oxidative addition of trifluoroacetophenone to 2 at 70 °C, 10 was formed. Compound 1 was subjected to an X-ray crystal structure analysis; the two independent molecules differ in the side-chain conformation.