“One‐pot” synthesis of (<i>Z</i>)‐2‐aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via hexamethylphosphoramide‐promoted sequential transformation

Reaction of the methylene diphosphonates [(RO)2P(O)]2CH2, where R = iPr or Et, with the metalating reagents NaH, nBuNa or the superbasic mixture tBuONa/nBuLi leads to monodeprotonation, and formation of the complexes [{(iPrO)2P(O)}2CHNa]4 (1) and [{(EtO)2P(O)}2CHNa]6 (2). Single‐crystal X‐ray diffraction studies revealed that 1 is tetrameric in the solid state, with a central Na4O4 cubane core. Each metal in 1 is rendered pentacoordinate by binding to three μ3‐O phosphoryl bridges within the cubane, a chelating phosphoryl unit, and also a single iPrO group. In contrast, the structure of 2 is hexameric, and is composed of an unusual six‐rung Na6O6 ladder core. Three distinct sodium environments as well as μ1‐, μ2‐ and μ3‐O phosphoryl units are present within the ladder framework. No Na−C interactions are present in either 1 or 2. All of the six‐membered NaOPCPO chelate rings display localized P=O double bonds and partial multiple bonding on the P−C−P linkages (mean P−O: 1.49 Å, and mean P−C: 1.69 Å). Ab initio molecular orbital calculations (HF/6−31G*) on model complexes indicate that the hexameric arrangement found for 2 is thermodynamically more stable than the cubane structure of 1, in the absence of steric effects. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

“One‐pot” synthesis of (Z)‐2‐aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via hexamethylphosphoramide‐promoted sequential transformation

Abstract: ( Z)-2-Aryl-1-(2-cyanoethyl)ethenylphosphonates were synthesized by the hexamethylphosphoramide-promoted sequential transformation of tetra-alkyl methanediphosphonates, by the action of potassium tert-butoxide, and then by acrylonitrile and aldehydes.

Cited by 2 publications

References 28 publications

ChemInform Abstract: “One‐Pot” Synthesis of (Z)‐2‐Aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via Hexamethylphosphoramide‐Promoted Sequential Transformation.

ChemInform Abstract: “One‐Pot” Synthesis of (Z)‐2‐Aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via Hexamethylphosphoramide‐Promoted Sequential Transformation.

Sodiated β‐Diphosphonate Carbanions: Characterization of the Tetrameric Cubane and the Hexameric Ladder Complexes [{(iPrO)₂P(O)}₂CHNa]₄and [{(EtO)₂P(O)}₂CHNa]₆

Contact Info

Product

Resources

About

“One‐pot” synthesis of (Z)‐2‐aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via hexamethylphosphoramide‐promoted sequential transformation

Abstract: ( Z)-2-Aryl-1-(2-cyanoethyl)ethenylphosphonates were synthesized by the hexamethylphosphoramide-promoted sequential transformation of tetra-alkyl methanediphosphonates, by the action of potassium tert-butoxide, and then by acrylonitrile and aldehydes.

Cited by 2 publications

References 28 publications

ChemInform Abstract: “One‐Pot” Synthesis of (Z)‐2‐Aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via Hexamethylphosphoramide‐Promoted Sequential Transformation.

ChemInform Abstract: “One‐Pot” Synthesis of (Z)‐2‐Aryl‐1‐(2‐cyanoethyl)ethenylphosphonates via Hexamethylphosphoramide‐Promoted Sequential Transformation.

Sodiated β‐Diphosphonate Carbanions: Characterization of the Tetrameric Cubane and the Hexameric Ladder Complexes [{(iPrO)2P(O)}2CHNa]4and [{(EtO)2P(O)}2CHNa]6

Contact Info

Product

Resources

About

Sodiated β‐Diphosphonate Carbanions: Characterization of the Tetrameric Cubane and the Hexameric Ladder Complexes [{(iPrO)₂P(O)}₂CHNa]₄and [{(EtO)₂P(O)}₂CHNa]₆