6840-01-3Relevant academic research and scientific papers
Reduction of λ5-Phosphinines
Savateev, Aleksandr,Vlasenko, Yurii,Shtil, Nataliya,Kostyuk, Aleksandr
supporting information, p. 628 - 632 (2016/03/01)
A convenient method to easily prepare parent λ3-phosphinine from easily accessible λ5-precursors was developed. A series of λ5-phosphinines bearing heteroatom substituents OMe, SMe, and/or NMe2 at the phosphorus
Preparation of various carboxylic acid esters from bulky alcohols and carboxylic acids by a new type oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone
Mukaiyama, Teruaki,Kikuchi, Wataru,Shintou, Taichi
, p. 300 - 301 (2007/10/03)
A new-type oxidation-reduction condensation by using 2,6-dimethyl-1,4-benzoquinone (DMBQ), carboxylic acids and in situ formed alkoxydiphenylphosphines (1) including the bulky alkoxy group-substituted ones proceeded smoothly to afford the corresponding carboxylic acid esters in good to high yields. Alkoxydiphenylphosphines were formed in situ by treating either N,N-dimethylaminodiphenylphosphine (Ph2PNMe2) with primary or secondary alcohols or chlorodiphenylphosphine with the lithium salts of primary, secondary and tertiary alcohols.
Efficient method for the preparation of carboxylic acid alkyl esters or alkyl phenyl ethers by a new-type of oxidation-reduction condensation using 2,6-dimethyl-1,4-benzoquinone and alkoxydiphenylphosphines
Shintou, Taichi,Kikuchi, Wataru,Mukaiyama, Teruaki
, p. 1645 - 1667 (2007/10/03)
A new-type of oxidation-reduction condensation proceeded smoothly to afford carboxylic acid alkyl esters or alkyl phenyl ethers in good to high yields by combined use of alkoxydiphenylphosphines (1) having primary, bulky secondary or tertiary alkoxy groups, a mild quinone-type oxidant such as 2,6-dimethyl-1,4-benzoquinone (DMBQ) and carboxylic acids or phenols. Generally, alkoxydiphenylphosphines were prepared easily from chlorodiphenylphosphine (2) and alcohols in the presence of pyridine, and were isolated by distillation. On the other hand, the phosphines 1 were also prepared in situ from N,N-dimethylaminodiphenylphosphine (3a) and primary or secondary alcohols while primary, bulky secondary or tertiary alkoxydiphenylphosphines were alternatively formed in situ by adding 2 to the "BuLi-treated alcohols in order to perform the above reactions by a one-pot procedure from alcohols and nucleophiles. The reaction of thus formed 1, DMBQ and carboxylic acids or phenols afforded the corresponding alkylated products, including hindered secondary and tertiary alkylated ones, in good to high yields at room temperature. In the case of using chiral secondary alcohols, the corresponding carboxylic acid alkyl esters were obtained as well in high yields with perfect inversion of stereochemistry by SN2 replacement.
The Mechanism of Double Olefination Using Titanium-Substituted Ylides
Reynolds, Kelly A.,Finn
, p. 2574 - 2593 (2007/10/03)
The adduct 3, derived from TiCl3(OiPr) and (Me2N)3P=CH2, engages in a complicated set of interactions with NaN(SiMe3)2 and aldehydes, resulting in the requirement to use excess amounts of both reagents for the one-pot synthesis of allenes. When TiCl2(OiPr)2 is used instead, ligand substitution reactions with NaN(SiMe3)2 are diminished and so stepwise transformations can be accomplished without excess amounts of each reagent. The selective production of vinylphosphonium salts and byproduct titanium oxides from Ti-substituted ylides and aldehydes is proposed to arise from the presence of a chloride leaving group on the metal. Isolated vinylphosphonium compounds may be deprotonated with phenyllithium to give thermally sensitive allenic phosphoranes, which have been characterized by low temperature multinuclear NMR. The reaction of allenic phosphoranes with aldehydes affords oxaphosphetane and betaine intermediates which appear to interconvert upon warming to produce allene and phosphine oxide. Dimethylamino-substituted phosphorus components are required for high yields in both steps of the allene-forming process, presumably to boost the reactivity of the hindered Ti-substituted ylide reagents and to stabilize the allenic phosphorane unit so that it may be trapped by aldehyde. The placement of chiral groups on the phosphorus methylide or aldehyde components results in low levels of enantiomeric and diastereomeric induction, respectively, during allene formation. In two cases, the diastereomeric ratios of initially-formed oxaphosphetanes have been found to differ from the diastereomeric composition of their product allenes, offering examples of the phenomenon known as "stereochemical drift". However, oxaphosphetane/betaine formation from allenic phosphorane and aldehyde has been found to be irreversible, suggesting that an intramolecular betaine olefin isomerization is responsible for the loss of stereochemical integrity during the Wittig step.
DIMERISATION DE DIENES CONJUGUES A L'AIDE DE COMPLEXES DU NICKEL EN PRESENCE DE LIGANDS DE TYPE AMINOPHOSPHINITE ETUDE D'OPTIMISATION
Masotti, Henriette,Pfeiffer, Gilbert,Siv, Chhan,Courbis, Pierre,Sergent, Michelle,Phan TAN LUU, Roger
, p. 63 - 77 (2007/10/02)
New chiral aminophosphinite ligands are readily prepared and their behaviour as homogeneous catalysts was investigated in the linear dimerization of butadiene and isoprene.This latter reaction has been optimised using experimental research methodology, leading to a conversion rate above 50percent.
UEBER DIE INSERTION VON RPS2 IN DIE PN-BINDUNG VON AMINOPHOSPHINEN
Diemert, K.,Hein, G.,Janssen, A.,Kuchen, W.
, p. 339 - 356 (2007/10/02)
Aminophosphines RnP(NR'2)3-n (n = 2, 1, 0; R = Ph, c-Hex, (-)Men, t-Bu; R' = Me, Et, n-Bu) react with 2,4-Bis(aryl)-1,3,2,4-dithiadiphosphetane-2,4-disulfides (ArPS2) (Ar: Ph, 4-Methoxyphenyl = An, Naphthyl, Thienyl) under formal insertion of monomeric (ArPS2)-units in one or in two of the λ3-P-N-bonds to yield chiral organophosphorus compounds Ar(R'2N)P(S)-S-PRn(NR'2)2-n (n = 2, 1, 0) and 2PRn(NR'2)1-n (n = 1, 0).At room temperature chiefly the λ3-P-N and λ3-P-S bonds in these products are solvolyzed by H2O or methanol with formation of mixtures of compounds.With hydrogen chloride An(Et2N)P(S)-S-PPh(NEt2) is converted into An(Et2N)P(S)-S-PPh(Cl).Addition of sulfur yields Ar(R'2N)P(S)-S-P(S)Rn(NR'2)2-n (n = 2, 1).Stereoisomerism of the new compounds is discussed and their structures as well as the composition of reaction mixtures are deduced from 31P-NMR-spectra.
SYNTHESE UND SPEKTROSKOPISCHE CHARAKTERISIERUNG VON CYCLOPENTADIENYLEISEN-KOMPLEXEN MIT P-N-LIGANDEN DES TYPS (C6H5)3-nP(NR2)N (n = 0-3; R = CH3, C2H5)
Schumann, Hans
, p. 169 - 178 (2007/10/02)
The complex cations BF4 (L = (C6H5)3-nP(NR2)n; n = 0-3; R = CH3, C2H5) have been obtained from the reaction of BF4 (I) with L.The reaction of I with E(NR2)3 (E = As, Sb; R = CH3) is also described.Spectroscopic investigations (IR, 1H, 13C and 31P NMR) indicate an increase in electron density on the iron center through increase of the number of P-bound NR2 groups.
Etude par la resonance de l'azote 15 et du phosphore 31 de la liaison P-N dans des derives du phosphore trivalent; analyse statistique des donnees experimentales
Gouesnard, Jean-Paul,Dorie, Jean,Martin, Gerard J.
, p. 1295 - 1304 (2007/10/02)
Natural abundance 15N and 31P nmr and dynamic 13C nmr have been applied to the study of about fifty aminophosphines, in order to generalize the influence of the chemical factors which govern the electronic distribution of the nitrogen-phosphorus III bond.
