Synthesis and Characterization of Alkoxy Spirophosphoranes Prepared from Hydrospirophosphoranes and Sodium Alcoholates

Abstract

The Atherton–Todd‐type reaction of hydrospirophosphoranes (HSPs) and sodium alcoholates was investigated. Direct alkoxylation of HSPs was accomplished with sodium alcoholates in acetonitrile under nitrogen atmosphere. The stereochemistry mechanism of the alkoxidation of HSPs was proposed by the 31P NMR tracing experiment. The reaction proceeded via the chlorinated spirophosphorane intermediate with stereoretention of the configuration at phosphorus, followed by the rear and front attack of alkoxide anions to produce alkoxy spirophosphoranes. The reaction mechanism well explained the results of the reaction of HSPs with sodium alcoholates.

Synthesis, crystal structure and hydrolysis of novel isomeric cage (P–C/P–O)-phosphoranes on the basis of 4,4,5,5-tetramethyl-2-(2-oxo-1,2-diphenylethoxy)-1,3,2-dioxaphospholane and hexafluoroacetone

“…Hz, H 21,23 ), 7.44 (m, 2H, XX 0part of AMM 0 XX 0 -system, 3 J XM ¼ 3 J X 0 M 0 ¼ 7.5 Hz, H 14,18 ), 7.32 (br dd, 2H, MM 0 -part of AMM 0 XX 0 -system, 3 J XM ¼ 3 J X 0 M 0 ¼ 7.…”

“…Therefore, the synthesis, structure and chemical transformations of phosphoranes have attracted considerable attention. [20][21][22][23][24][25][26][27] Among the diverse synthetic methods for the preparation of phosphoranes, several general approaches based on the addition reactions of P(III)-derivatives to unsaturated systems, various reactions of tetracoordinated phosphorus and substitution reactions at P(V) 28,29 should be noted.…”

Chiral Hypervalent, Pentacoordinated Phosphoranes

“…It was found, upon optimization of the reaction conditions, that the spirophosphoranes 137a,b gave the pure diasteroisomer of pyrospirophosphoranes 142a,b whereas a mixture of diastereoisomers 141c-e and 143c-e were isolated if hydrospirophosphoranes 137c-e were used as substrates. A series of the alkoxy spirophosphoranes 144,145 was also prepared by this approach (Scheme 60) but unfortunately as a mixture of diastereoisomers (in most cases in 1:1 ratio) [117]. Bicyclic hydrophosphoranes 147 and 148 were synthesized as a 3:2 mixture of two epimers by the reaction of tris-(N,N-diethyl)phosphorus amide with isoleucinol 146.…”

“…The isolated spirophosphoranes 147-149 were used as chiral ligands in the Pdcatalyzed alkylation of 1,3-diphenyl allyl acetate with acceptable stereoselectivity (up to 74% ee) (Scheme 61) [119]. Moreover, these hydrophosphorane derivatives were used to obtain complexes with [Pt ( A series of the alkoxy spirophosphoranes 144,145 was also prepared by this approach (Scheme 60) but unfortunately as a mixture of diastereoisomers (in most cases in 1:1 ratio) [117]. A series of the alkoxy spirophosphoranes 144,145 was also prepared by this approach (Scheme 60) but unfortunately as a mixture of diastereoisomers (in most cases in 1:1 ratio) [117].…”

“…Moreover, these hydrophosphorane derivatives were used to obtain complexes with [Pt ( A series of the alkoxy spirophosphoranes 144,145 was also prepared by this approach (Scheme 60) but unfortunately as a mixture of diastereoisomers (in most cases in 1:1 ratio) [117]. A series of the alkoxy spirophosphoranes 144,145 was also prepared by this approach (Scheme 60) but unfortunately as a mixture of diastereoisomers (in most cases in 1:1 ratio) [117]. Bicyclic hydrophosphoranes 147 and 148 were synthesized as a 3:2 mixture of two epimers by the reaction of tris-(N,N-diethyl)phosphorus amide with isoleucinol 146.…”