Communication
ChemComm
Table
3
Hydrophosphination of cyclohexene and norbornene with
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PhPH2 and Ph2PH catalyzed by 1a
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No. Alkene Phosphine Product
1
Time (h) Conv.c,d,e (%)
96
168
53
62b
PhPH2
2
3
96
168
69
73b
Ph2PH
4
¨
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5
PhPH2
Ph2PH
48
48
84
89
6
a
Reaction in neat substrates [phosphine]0 : [olefin]0 : [1]0 = 20 : 20 : 1,
b
[precat]0 = 190.0 mM, T [1C] = 70. [phosphine]0 : [cyclohexene]0 : [1]0
20 : 80 : 1 [1]0 = 70.0 mM; T [1C] = 90. Conversion of phosphine,
=
c
d
determined by NMR spectroscopy. Chemoselectivity was determined
by 31P{1H} NMR spectroscopy. Regioselectivity was determined by 1H,
e
31P{1H} NMR spectroscopy.
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31 A. A. Kissel, T. V. Mahrova, D. M. Lyubov, A. V. Cherkasov,
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a catalyst enabling a highly challenging transformation –
hydrophosphination of normally inert 1-alkenes. The most
promising results were obtained for 1 which provides excellent
conversion: up to 81% for 1-alkene, 73% for cyclohexene and
89% for norbornene. Moreover, for the hydrophosphination of
1-alkenes with PhPH2 excellent regio- and chemoselectivities
are observed. The possibility of a rare-earth mediated hydro-
phosphination of cyclohexene and norbornene with both
PhPH2 and Ph2PH was demonstrated for the first time. Studies
aimed at enlarging the reaction scope to various types of
substrates as well as mechanistic and kinetic studies are
currently underway.
This work was supported by the Russian Foundation for
Basic Research (Grant No. 19-33-90273).
´
´
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Conflicts of interest
There are no conflicts to declare.
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