319488-97-6

Upstream product

• 105625-06-7 (1-methyl-pentyl)-diphenyl-phosphane 
• 1516-56-9 azidoformiate de methyle 
• 127802-82-8 P-(ethyl)-P,P-(diphenyl)(N-methoxycarbonyl)phosphazene 
• 3377-86-4 2-bromohexane 
• 127802-81-7 P,P-diphenyl-P-(methyl)(N-methoxycabonyl)phosphazene 
• 603-35-0 triphenylphosphine 
• 109-65-9 1-bromo-butane 
• 607-01-2 ethyl-diphenyl-phosphane 

Downstream Products

• 60428-22-0 (Z)-(2-methylhex-1-enyl)benzene 
• 60428-21-9 (E)-(2-methylhex-1-enyl)benzene 

Relevant academic research and scientific papers

Synthesis of Pentacoordinated Spiro[44]phosphoranes by Reaction of Cyclic Phosphazenyl Anions with Epoxides: Study of their P-Remote Functionalization and Hydrolysis

The synthesis of a new family of pentacoordinated spiro[4.4]phosphoranes stabilized by the ortho-benzamide bidentate ligand (oBA, -C6H4-2-C(O)NH-) through reaction of C,Cortho-dilithiated phosphazenes with oxiranes is reported. Mixtures of epimers that differ in configuration at the phosphorus atom were obtained with moderate to high yields and diastereoselectivities. C3-Disubstituted derivatives could be separated, which provided access to enantiopure products arising from the reaction with (R)-2-phenyloxirane. Stereomutation was observed by heating the spirophosphoranes at 100 C. Directed ortholithiation of spirophoshoranes followed by electrophilic quench reactions including carbon-based and heteroatom-based electrophiles afforded derivatives functionalized in a remote position with respect to the phosphorus atom. Benzoic acid catalyzed hydrolysis of spirophosphoranes furnished ortho-(γ-hydroxyalkylphosphoryl)benzamides by cleavage of the P O and P N bonds with retention of the phosphorus configuration. In contrast, alkaline hydrolysis led to the formation of γ- hydroxyphosphinic acids and benzamide.

Reactions of lithiated P-diphenyl(alkyl)(N-methoxycarbonyl)phosphazenes with Michael acceptors and aldehydes. Synthesis of 1H-1,2-azaphosphinin-6-ones, β-hydroxy(N-methoxycarbonyl)phosphazenes and 5,6-dihydro-1,3,4-oxazaphosphinin-2-ones

Lithium (N-methoxycarbonyl)phosphazenes add C-regioselectively to DMAD, dimethyl malonate, fumarate, and butylidenmalonate in a [1,4] manner. Only one diastereoisomer is observed with the olefinic electrophiles. With DMAD the initial adduct evolves through cyclocondensation with the CO2Me group of the phosphazene and 1H-1,2-azaphosphinin-6-ones are obtained. Exceptionally, methyl phenylpropiolate reacted exclusively through the carbonyl yielding a mixture of C- and N-acylated compounds. The addition to aldehydes at -80°C affords β-hydroxyphosphazenes diastereoselectively. For lithium α,α-dimethyl(N-methoxycarbonyl)phosphazenes, the intermediate alkoxides cyclocondense at room temperature to 5,6-dihydro-1,3,4-oxazaphosphinin-2-ones.

Olefination reactions through phosphazenes

The first synthesis of di-, tri- and tetrasubstituted alkenes through reaction of lithium P-diphenyl(alkyl)(N-carboxymethyl)phosphazenes with aldehydes and ketones is reported.