Stereoselective PCO/POC-Rearrangement of P-C-Cage Phosphorane in the Reaction of 4,5-Dimethyl-2-(2-oxo-1,2-diphenyl)ethoxy-1,3,2-dioxaphospholane with Hexafluoroacetone.
Interaction of 4,5-dimethyl-2-(2-oxo-1,2-diphenyl)ethoxy-1,3,2-dioxaphospholane, bearing a carboxyl group in the γ-position with respect to the phosphorus atom and obtained from d,l-butanediol, with hexafluoroacetone (CCl4, -40 °C) leads to the simultaneous formation of regio- and stereoisomeric cage-like phosphoranes with phosphorus-carbon and phosphorus-oxygen bonds with a high stereoselectivity (>95%), whose structure was determined by 1D and 2D NMR spectroscopy and XRD. When stored as a solution in dichloromethane for one month, the PCO-isomer rearranges into the thermodynamically more stable POC-isomer of the cage-like phosphorane. Mild hydrolysis of the PCO/POC-isomers proceeds with a high chemoselectivity and leads to the formation of P(IV)-dioxaphospholane derivatives. Acidic hydrolysis of the POC-isomer leads to the formation of an oxirane derivative with an unexpectedly high stereoselectivity (>95%). DFT calculations (using the PBE functional) allowed us to obtain structures and energies of the initial phospholane, reaction products (PCO/POC-isomers), and an intermediate P(V)-oxaphosphirane.
A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences , Arbuzov str. 8, Kazan 420088, Russian Federation.
Vladimir F
VF
Mironov
A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences , Arbuzov str. 8, Kazan 420088, Russian Federation.
Mudaris N
MN
Dimukhametov
Institute of Physics, Kazan Federal University , Kremlevskaya str. 18, Kazan 420008, Russian Federation.
Sergey V
SV
Efimov
Institute of Physics, Kazan Federal University , Kremlevskaya str. 18, Kazan 420008, Russian Federation.
Roza M
RM
Aminova
Institute of Physics, Kazan Federal University , Kremlevskaya str. 18, Kazan 420008, Russian Federation.
Farida Kh
FKh
Karataeva
A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences , Arbuzov str. 8, Kazan 420088, Russian Federation.
Dmitry B
DB
Krivolapov
A.E. Arbuzov Institute of Organic and Physical Chemistry of the Russian Academy of Sciences , Arbuzov str. 8, Kazan 420088, Russian Federation.
Ekaterina V
EV
Mironova
Institute of Physics, Kazan Federal University , Kremlevskaya str. 18, Kazan 420008, Russian Federation.
Vladimir V
VV
Klochkov