116972-70-4

Upstream product

• 61300-75-2 phenylphosphine pentacarbonyltungsten⁽⁰⁾ 
• 814-49-3 diethyl chlorophosphate 
• 4111-54-0 lithium diisopropyl amide 
• 88000-32-2 (1,2-diphenylphosphirane)pentacarbonyltungsten 
• 17052-29-8 bis((O,O-diethyl)phosphonato)-phenylphosphine 
• 136986-77-1 bis((O,O-diethyl)phosphonato)phenylphosphine tungsten pentacarbonyl 
• 7732-18-5 water 
• 14040-11-0 tungsten hexacarbonyl 

Downstream Products

• 117064-22-9 (phenylisobutylidenephosphine)pentacarbonyltungsten 
• 116972-71-5 (CO)5WP(C(CH₃)2)(C₆H₅) 
• 116972-72-6 (CO)5WP(C(CH₂)4)(C₆H₅) 
• 124992-34-3 {1-phenyl-2-(2-thienyl)-4,5-dimethyl-1,2,3,6-tetrahydrophosphorine}pentacarbonyltungsten 
• 125472-29-9 P(C₆H₅)C₅H₅(CH₃)2(C₂H(CH₃)C₂H₄CHC(CH₃)2)W(CO)5 
• 124992-32-1 ((C₆H₅)PHC(CH₃)CH₂)W(CO)5 
• 125074-78-4 {methyl (2-oxo-1-methylpropyl)phenylphosphinite}pentacarbonyltungsten 
• 127899-29-0 W(CO)5(C₆H₅PC(CO₂C₂H₅)2) 
• 1355997-33-9 ((CO)5WP(C₆H₅)C(CH₃)2)2 
• 1446498-26-5 C₂₅H₁₅O₅PW 
• 1446498-28-7 C₂₅H₁₃O₅PW 
• 1446498-34-5 C₂₆H₁₉O₆PW 
• 1446498-24-3 C₂₉H₂₆O₉P₂W 
• 1446498-20-9 C₂₉H₂₆O₉P₂W 

Relevant academic research and scientific papers

Revisiting the phospha-Wittig-Horner reaction

P,P-Dichlorophosphines 2a-c (RPCl2, R = Ph (a), t-Bu (b), 2,4,6-Me3Ph (c)) and P,P-dibromophosphines 4d,e (RPBr2, R = (i-Pr)3SiC≡C (d) and H2C=CH (e)) react with triethylphosphite under Michaelis-Arbuzov conditions to give phosphinodiphosphonates 3a-e in quantitative yields. After complexation to W(CO)5 and treatment with CH3ONa, phospha-Wittig-Horner reagents 9a,b are obtained on a multigram scale in good overall yield. Phospha-Wittig-Horner reagents with unsaturated substituents at IIIP (10d,e) can be prepared in analogous procedures; however, they prevail in an unusual ylide form that allows conjugation between the lone pair and the acetylene and vinyl π-systems, respectively. Phosphinophosphonate 9a has been characterized by X-ray crystallography and is shown to react smoothly with acetone within minutes. The resulting W(CO)5-coordinated phosphaalkene is shown to dimerize to a 1,2-diphosphitane or to undergo a 1,3-proton shift depending on the reaction conditions. In addition, a one-pot synthetic sequence starting from W(CO)5-coordinated phosphinodiphosphonates 5d,e has been developed to engage compounds with vinyl and acetylene substituents in phospha-Wittig-Horner reactions.

The "phospha-Wittig" reaction: A new method for building phosphorus-carbon double and single bonds from carbonyl compounds

The so-called "phospha-Wittig" reagents [(EtO)2P(O)PHR]M(CO)5 (M = Mo, W) are obtained via the reaction of primary phosphine complexes (RPH2)M(CO)5 with lithium diisopropylamide and diethyl chlorophosphate. The corresponding anions [(EtO)2P(O) - P-R]M(CO)5 react with carbonyl compounds under mild conditions to give the phosphaalkene complexes [R1R2C=PR]M(CO)5. A study of this reaction with R = Ph, R1 = i-Pr, and R2 = H has shown that the kinetic product is the (Z)-phosphaalkene complex, whereas the thermodynamic product is the E isomer. The stereochemistry of these complexes was established by X-ray crystal structure analysis. With α-diketones, only one carbonyl bond is converted into a P=C double bond, probably for steric reasons. Most of the phosphaalkene complexes thus obtained easily react with methanol or 2,3-dimethylbutadiene. The phosphane-Mo(CO)5 complexes synthesized via such a scheme are easily transformed into the corresponding P-sulfides by simple heating with sulfur in toluene. Thus, the "phospha-Wittig" reaction can also be viewed as a new tool for building organophosphorus species with P - C single bonds.