76263-88-2

Upstream product

• 98-85-1 1-Phenylethanol 
• 2524-64-3 chlorophosphoric acid diphenyl ester 
• 2425-28-7 2-Bromo-1-phenylethanol 

Downstream Products

• 143238-89-5 tert-butyl 2-methylene-4-phenylpentanoate 
• 4769-42-0 9-(1-phenylethyl)-9H-fluorene 
• 94871-36-0 1,1,2-Triphenylpropane 
• 93-96-9 bis(1-phenylethyl)ether 

Relevant academic research and scientific papers

Organocatalytic phosphorylation of alcohols using pyridine- N -oxide

Phosphorylation of alcohols by phosphoryl chlorides catalysed by pyridine-N-oxide is reported. The utility of this method is demonstrated through phosphorylation of primary, secondary and a tertiary alcohol as well as phenols under mild reaction conditions and with low catalyst loading (5 mol%).

Substitution- and elimination-free phosphorylation of functionalized alcohols catalyzed by oxidomolybdenum tetrachloride

Among 14 oxidometallic species examined for catalytic phosphorylation of the tested alcohols, oxidomolybdenum tetrachloride (MoOCl4) was found to be the most efficient with a negligible background reaction mediated by triethylamine (Et3N). The new catalytic protocol can be applied to the chemoselective phosphorylations of primary, secondary and tertiary alcohols as well as the substitution-free phosphorylations of allylic, propargylic, and benzylic alcohols. Functionalized alcohols bearing acetonide, tetrahydropyranyl ether, tert-butyldimethylsilyl ether, or ester group are also amenable to the new catalytic protocol. The most difficult scenarios involve substitution-free phosphorylations of 1-phenylethanol and 1-(2-naphthyl)ethanol which can be effected in 95 and 90% yields, respectively. ESI-MS, IR, 1H, and 31P NMR spectroscopic analyses of the reaction progress suggest the intermediacy of an alkoxyoxidomolybdenum trichloride-triethylamine adduct such as [(RO)Mo(O)Cl3-Et3N] to be responsible for the catalytic turnover.

Stereochemical consequences of the use of chiral N-phosphoryl oxazolidinones in the attempted kinetic resolution of bromomagnesium alkoxides

A number of chiral N-phosphoryl oxazolidinones have been prepared and evaluated as asymmetric phosphoryl transfer agents with the magnesium alkoxide of 1-phenyl ethanol. The reaction proceeded with little stereoselection, which was shown to be a consequence of the reaction mechanism that occurs with inversion of configuration at phosphorus consistent with in-line attack opposite the leaving group.

Catalytic phosphorylation using a bifunctional imidazole derived nucleophilic catalyst

A bifunctional catalyst containing a polyether backbone and a nucleophilic imidazole moiety has been prepared that demonstrates cooperative catalysis in the presence of added group 1 and 2 salts for the phosphorylation of alcohols. The Royal Society of Chemistry 2005.

Design, synthesis, application and recovery of a minimally fluorous diaryl diselenide for the catalysis of stannane-mediated radical chain reactions

The synthesis of a minimally fluorous (52% F) diaryl diselenide is described. On reduction in situ with tributylstannane this diselenide provides a fluorous selenol which is effective in inhibiting a range of stannane-mediated radical rearrangements, including a cyclopropylcarbinyl ring opening. A method for the recovery of the fluorous diselenide involving continuous extraction in a modified, cooled continuous extractor is described.

Inhibition of stannane-mediated radical rearrangements by a recoverable, minimally fluorous selenol

(equation presented) The preparation of a minimally fluorous diaryl diselenide is described. It is demonstrated that this diselenide, reduced in situ to the corresponding selenol, may be used in conjunction with stannanes to prevent a number of radical rearrangements. A 1 M solution of this selenol used in admixture with Breslow's water-soluble stannane can be used to significantly inhibit a cyclopropylcarbinyl ring opening. The combination of the fluorous selenol and the polar stannane permits recovery of the selenol by continuous fluorous extraction and isolation of a stannane-free hydrocarbon product.

The β-(phosphatoxy)alkyl radical rearrangement. Rate constants, arrhenius parameters, and structure activity relationships

Rate constants for the migration of a series of p,p-disubstituted β-(diarylphosphatoxy)alkyl migrations have been determined in benzene at reflux by competition against the benzeneselenol clock reaction. There is a strong linear correlation of log(k) with

Chemistry of β-(phosphatoxy)alkyl and β-(acyloxy)alkyl radicals. Migration reactions: Scope and stereoselectivity of β-(phosphatoxy)alkyl rearrangement. Mechanism of β-(phosphatoxy)alkyl and β-(acyloxy)alkyl migration

An in depth study of the mechanism of the β-(phosphatoxy)alkyl radical migration is presented. Examples are presented which define the scope and limitations of the migration and show that, in certain cases, it is highly stereoselective. It is shown that phosphoranyl radicals are not intermediates in this rearrangement. A series of experiments with stereochemically-, 18O-, and deuterium-labeled probes indicate that the migration is intramolecular, proceeds through competing 1,2- and 2,3-pathways, and does not involve fragmentation to a cage pair followed by recombination. The deuterium-labeled probe is also applied to the β-(acyloxy)alkyl migration with the same result. The changing proportions of 1,2- and 2,3-shifts in going from the β-(phosphatoxy)alkyl to the β-(acyloxy)alkyl migration are discussed in terms of the conformational equilibria of the two different esters and the Curtin-Hammett principle.

Inhibition of Rearrangements in Stannane-Mediated Radical Reduction Reactions by Catalytic Quantities of Diphenyl Diselenide. An Example of Polarity Reversal Catalysis

The presence of only 10 mol percent of PhSeH, PhSeSePh (reduced in situ to PhSeH), and, to a lesser extent, PhSH has a dramatic effect on the efficiency of stannane-mediated free radical rearrangement reaction owing to the superior hydrogen donating qualities of PhSeH and PhSH.Slow radical rearrangements can be prevented altogether, and the yields of even moderately rapid rearrangements significantly diminished.The addition of 10 mol percent of PhSeSePh to stannane-mediated aryl radical cyclizations is advantageous as the initial, rapid, 5-hexenyl rearrangement is not impaired but the subsequent, slower neophyl rearrangement is effectively minimized, resulting in the formation of vastly improved 5-exo/6-endo ratios.