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Unusual Ring‐Closure Reactions During the Oxidation of 1,1′‐Bi(3‐methylphosphol‐2‐ene) with Hexafluoroacetone — Formation of a Tricyclic Fluorine‐Containing Phosphorane
Author(s) -
Vollbrecht Sebastian,
Vollbrecht Alexander,
Jeske Jörg,
Jones Peter G.,
Schmutzler Reinhard,
Du Mont WolfWalther
Publication year - 1997
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19971300623
Subject(s) - chemistry , phosphorane , hexafluoroacetone , medicinal chemistry , adduct , ene reaction , trigonal bipyramidal molecular geometry , magnesium , stereochemistry , crystallography , crystal structure , organic chemistry
Reduction of the isoprene—PCl 3 adduct 1 with magnesium powder, or with Si 2 Cl 6 , furnished P ‐chloro‐3‐methyl‐phosphol‐2‐ene, 2 , in satisfactory yield. Further reduction of 2 with Si 2 Cl 6 gave the new trichlorosilyl‐3‐methylphosphol‐2‐ene, 3 . The reaction of 2 with magnesium powder, with 3 , or with 1/2 equivalent of Si 2 Cl 6 provided the new γ 3 P‐γP‐diphosphane 1,1′‐bi(3‐methylphosphol‐2‐ene) 4 . Reduction of 4 with Si 2 Cl 6 led to 3 . Oxidation of 4 with selenium gave the 1,2‐diphosphane diselenide, 5 . The oxidation of 4 with hexafluoroacetone led to a mixture of products, from which a novel tricyclic phosphorane 6 was separated. the structure of 196 was determined by X‐ray diffraction; the coordination geometry at phosphorus in distorted trigonal bipyramidal, with a very long equatorial P—C(CF 3 ) 2 bond of 193.2(2) pm.