The first structural study on a cyclic tricoordinate phosphorochloridite and a pentacoordinate phosphorane based on 1,2,3,5-protected myo-inositol--a new conformation of 1,3,2-dioxaphosphorinane ring.
Treatment of the phosphoramidite [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)P-NH-i-Pr)] with o-chloranil affords the first example of inositol-based pentacoordinate phosphorane [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)P-NH-i-Pr)(1,2-O(2)C(6)Cl(4))] (9) (X-ray structure) with a trigonal bipyramidal geometry at phosphorus. The six-membered 1,3,2-dioxaphosphorinane ring with the inositol residue has an unusual boat conformation in 9 which is quite different from that found in unrestrained rings investigated before, but is similar to that of its P(III) chloro precursor [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(O(2)PCl)] (X-ray structure). Also, a convenient and chromatography-free procedure for the protected myo-inositol derivative [myo-C(6)H(6)-2-[OC(O)Ph]-1,3,5-(O(3)CH)-4,6-(OH)(2)] is reported.
Pavan Kumar
K V P
KV
School of Chemistry, University of Hyderabad, Hyderabad 500 046, AP, India.
Kumara Swamy
K C
KC
D002236:Carbohydrate Conformation; D002703:Chloranil / Q000031:analogs & derivatives / Q000737:chemistry; D007294:Inositol / Q000737:chemistry*; D008968:Molecular Conformation; D015394:Molecular Structure; D010753:Phosphoranes / Q000138:chemical synthesis* / Q000737:chemistry*; D013237:Stereoisomerism
D010753:Phosphoranes; D002703:Chloranil; D007294:Inositol; C039499:2-chloranil