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Scheme 6 Synthesis of P-stereogenic diphosphines (SP,RP)-11a and
(SP,RP)-11b.
atoms leading to P-stereogenic diphosphine with absolute con-
figuration SP (P1) and RP (P2).
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34 N. Vinokurov, A. Michrowska, A. Szmigielska, Z. Drzazga, G.
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A P-stereogenic phosphine-borane is usually treated with an
excess of amine to give after filtration the pure phosphine with
complete retention of configuration at phosphorus.9,50,51 Reaction
of the P-stereogenic diphosphine diboranes (SP,RP)-10a and
(SP,RP)-10b with 1,4-diazabicyclo[2.2.2]octane (DABCO) in
toluene led to P-stereogenic diphosphines (SP,RP)-11a and
(SP,RP)-11b in 87 and 88% yield, respectively, which were virtually
pure according to their 1H, 13C, 31P NMR spectra (Scheme 6).
In conclusion, we have developed an approach to novel
C,P-stereogenic diphosphines by asymmetric 1,3-dipolar
cycloaddition and stereospecific reduction reaction sequence.
Asymmetric catalysis based on these novel C,P-chiral ligands
is underway in our laboratories.
35 N. Vinokurov, J. R. Garabatos-Perera, Z. Zhao-Karger, M.
Wiebcke and H. Butenschon, Organometallics, 2008, 27,
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1878–1886.
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This research was kindly supported by the Gottlieb Daimler-
and Karl Benz-Foundation (doctoral fellowship to N.V.) and by
the Deutsche Forschungsgemeinschaft.
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40 The s-cis conformation as the preferred ground state conformation
of vinyl phosphine oxides was already documented and was also
implied as the reactive conformation of vinyl phosphine oxides in
their 1,3-dipolar cycloaddition reactions with nitrones. A similar
distorted s-cis conformation of either OQP–CQC group has also
been found for (SP,SP)-6 using X-ray crystallography: N.
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