52224-89-2

Upstream product

• 1517-69-7 (R)-1-phenylethanol 
• 14593-46-5 sodium tert-pentoxide 
• 74-88-4 methyl iodide 
• 420-37-1 trimethoxonium tetrafluoroborate 
• 77-78-1 dimethyl sulfate 
• 67-56-1 methanol 
• 1459-15-0 (R)-1-chloro-1-phenylethane 
• 108-95-2 phenol 
• 207573-11-3 (1R,3S,4S)-3-((S)-2-Methoxy-2-phenyl-ethylselanyl)-1,7,7-trimethyl-bicyclo[2.2.1]heptan-2-one 
• 100-42-5 styrene 

Downstream Products

• 4809-56-7 N-(1-phenylethyl)-p-toluenesulfonamide 

Relevant academic research and scientific papers

Gold-catalyzed substitution reaction with ortho-alkynylbenzoic acid alkyl ester as an efficient alkylating agent

ortho-Alkynylbenzoic acid alkyl esters behave as alkylating agents in combination with gold catalysts. The reaction with alcohols occurs smoothly in the presence of catalytic amounts of Ph3PAuCl and AgOTf under mild conditions to produce the corresponding ether products in high yields. The protocol is also useful for Friedel-Crafts alkylation and N-alkylation of sulfonamides. The reaction likely proceeds through the gold-induced in situ construction of leaving groups and subsequent nucleophilic attack of nucleophiles, such as alcohols, aromatic compounds, and sulfonamides.

Asymmetric methoxyselenenylations and cyclizations with 3-camphorseleno electrophiles containing oxime substituents at C-2. Formation of an unusual oxaselenazole from an oxime-substituted selenenyl bromide

Di[(1R)-2-Oximo-endo-3-bornyl] diselenide (4) and its benzoate derivative 5 were prepared from the corresponding known 2-keto diselenide 1. Treatment of 4 and 5 with bromine, followed by silver triflate in methanol-dichloromethane, generated the corresponding selenenyl triflates 6b and 7b. The latter reagents reacted with a variety of mono-, di-, and trisubstituted alkenes to afford the corresponding 1,2-addition products (β-methoxy selenides) in a highly diastereoselective manner. The free oxime 6b was particularly effective in such methoxyselenenylations, giving diastereomeric ratios (d.r.s) ranging from 86:14 to > 98:2. Even cis-disubstituted alkenes, which typically give poor d.r.s in similar additions with other chiral selenium electrophiles, underwent highly stereoselective additions with this reagent. Reductive deselenizations of the adducts obtained from styrene and cis- and trans-stilbene provided the corresponding methyl ethers, whose absolute configurations were determined by comparison with authentic samples. As expected, the dominant enantiomers thus obtained from cis- and trans-stilbene, using either 6b or 7b, had opposite configurations. Moreover, each geometrical isomer of stilbene produced methyl ethers with the same configuration when treated with either the oxime 6b or the benzoate 7b. Coordination effects between the substituents at the 2-position of the camphor molecule and the positive selenium atoms in the intermediate seleniranium ions are believed to play an important role in determining the stereochemical outcome of methoxyselenenylations. Selenenyl triflate 6b and selenenyl chloride 7c were also investigated in the electrophilic cyclizations of several unsaturated alcohols and carboxylic acids. However, diastereoselectivities were typically much lower than in the methoxyselenenylations. When the selenenyl bromide 6a, derived from the addition of bromine to the corresponding diselenide 4, was allowed to stand in the absence of an alkene, it underwent intramolecular cyclization with the oxime hydroxyl group, followed by further bromination, to afford the unusual oxaselenazole 11, whose structure was determined by spectroscopic means as well as by X-ray crystallography.

Novel polymer-bound chiral selenium electrophiles

(equation presented) Polymer-bound chiral electrophilic selenium reagents have been developed and applied to stereoselective selenenylation reactions of various alkenes. Different cleavage protocols allow further functionalization of the addition products

New nitrogen containing chiral diselenides: Synthesis and asymmetric addition reactions to olefins

A simple synthesis of two new nitrogen containing diselenides, 7 and 8, is described. These compounds were employed as starting materials to effect the asymmetric methoxyselenenylation, the hydroxyselenenylation as well as the cyclofunctionalization of ol

Asymmetric electrophilic methoxyselenenylations and cyclizations with 3- camphorseleno derivatives

A series of novel 3-camphor-based diselenides, differing in substitution at C-2, was prepared. The corresponding allyl selenides were used as protecting groups for the diselenide moieties in several subsequent transformations. The diastereoselective methoxyselenenylation of alkenes was achieved with methanolic selenenyl triflates derived from the camphor diselenides, of which the 2-keto analogue proved the most effective. Diastereoselective electrophilic cyclizations of unsaturated alcohols, carboxylic acids and amides were most effectively performed with the corresponding selenenyl chloride, containing a spiro-oxazolidinone moiety at C-2 of the camphor residue. The absolute configurations of several products were determined by reductive deselenization.

Asymmetric selenomethoxylation of alkenes with camphorselenenyl sulfate

By reaction with ammonium persulfate the easily available diselenide derived from (1R)-(+)-camphor was converted into the camphorselenenyl sulfate. This chiral electrophilic selenium reagent reacted at room temperature with alkenes in the presence of methanol to afford selenomethoxylated adducts in good yields and with moderate to good facial selectivity. The two diastereomeric addition products could be separated in most cases.

Asymmetric methoxyselenenylations with camphor-based selenium electrophiles

The asymmetric methoxyselenenylation of olefins was achieved with a series of camphor-based selenenyl triflates, of which the readily available 2-oxo analog 2a proved the most effective.

Asymmetric addition reactions with optimized selenium electrophiles

The synthesis of various nonracemic diselenides by different methods is described. These diselenides are precursors for optically active selenium electrophiles. Their facial selectivity upon addition to styrene was investigated with respect to the chiral moiety neighboring the selenium. Diselenides 1i, 1n, and 1v yielded addition products 7 with diastereomeric excesses up to 95%. Some diselenides, intermediates, and products of the addition reaction were investigated by 77Se NMR spectroscopy.

Retentive Solvolysis. 16. Reinvestigation of the Retentive Phenolysis of 1-Phenylethyl Chloride. The Mechanism and the Structure of Ion Pair Intermediate

The effect added aniline on the polarimetric (kp) and titrimetric rate constants (kt) has been reexamined for the phenolysis of 1-phenylethyl chloride (RCl) in phenol-benzene (1:1 w/w).The kp-kt plot againts the

Chiral Phase-Transfer Catalysis. Enantioselective Alkylation of Racemic Alcohols with a Nonfunctionalized Optically Active Phase-Transfer Catalyst

Racemic sec-phenethyl alcohol and 1-phenyl-1-propanol can be alkylated to produce optically active methyl ethers in a phase-transfer-catalyzed reaction with dimethyl sulfate when the optically active quaternary ammonium salt 1 is used as the phase-transfer agent.