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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
Author(s) -
Borkenhagen Frank,
Neda Ion,
Thönnessen Holger,
Jones Peter G.,
Schmutzler Reinhard
Publication year - 1998
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/(sici)1521-3749(199804)624:4<650::aid-zaac650>3.0.co;2-8
Subject(s) - chemistry , imine , double bond , stereochemistry , oxidative addition , molecule , crystal structure , medicinal chemistry , polymer chemistry , crystallography , organic chemistry , catalysis
The reaction of aminomethyl dimethylphosphine oxide and (1 R)–(+)‐camphor furnished the σ 4 λ 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‐σ 5 λ 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.