86286-50-2

Usage

Preparation

To a stirred suspension of commercially available (10.0 g, 47 mmol) and triethylamine (14.4 mL, 0.10 mol) in dichloromethane (100 mL), diphosgene (3.0 mL, 25 mmol) was added dropwise at 0 °C and the mixture was stirred for 1 h at the same temperature. After concentration in vacuo, the residue was poured into water to precipitate crystals. The crystals were collected by filtration, successively washed with 10% HCl and H2O, and dried in vacuo at 50–60 °C for 3 h to afford 593a as colorless crystals (10.9 g, 97%).

InChI:InChI=1/C15H13NO2/c17-15-16-13(11-7-3-1-4-8-11)14(18-15)12-9-5-2-6-10-12/h1-10,13-14H,(H,16,17)/t13-,14+/m1/s1

Upstream product

• 54705-34-9 (1RS,2SR)-2-chloro-1,2-diphenyl-ethylamine; hydrochloride 
• 497-19-8 sodium carbonate 
• 1189-71-5 isocyanate de chlorosulfonyle 
• 1439-07-2 trans-Stilbene oxide 
• 530-36-9 2-amino-1,2-diphenylethanol 
• 32315-10-9 bis(trichloromethyl) carbonate 
• 530-36-9 threo-1,2-diphenyl-2-aminoethan-1-ol 
• 503-38-8 trichloromethyl chloroformate 
• 23364-44-5 (1S,2R)-2-Amino-1,2-diphenylethanol 
• 530-62-1 1,1'-carbonyldiimidazole 
• 105-58-8 Diethyl carbonate 
• 24424-99-5 di-tert-butyl dicarbonate 
• 124-38-9 carbon dioxide 
• 97-72-3 2-Methylpropionic anhydride 

Downstream Products

• 23204-71-9 (4R,5R)-trans-4,5-diphenyl-2-oxazolidinone 
• 170080-05-4 (4S,5S)-4,5-diphenyl-2-oxazolidinone 
• 86217-59-6 (4R,5S)-cis-4,5-Diphenyl-2-oxazolidone-3-carbamyl Chloride 
• 176692-16-3 (4R,5S)-3-(2-Bromo-acetyl)-4,5-diphenyl-oxazolidin-2-one 
• 211043-74-2 ethyl ((4R,5S)-2-oxo-4,5-diphenyloxazolidin-3-yl)acetate 
• 259097-06-8 benzyl {[(4R,5S),1S]2S}-2-chloro-2-[1-(2-oxo-4,5-diphenyl-3-oxazolidinyl)-spiropentyl]acetate 
• 494841-74-6 (4R,5S)-3-[(E)-3-(2-Chloro-pyridin-3-yl)-acryloyl]-4,5-diphenyl-oxazolidin-2-one 
• 880767-53-3 (4R,5S)-3-acetyl-4,5-diphenyloxazolidin-2-one 
• 256382-75-9 (4R,5S)-4,5-Diphenyl-3-prop-2-ynyl-oxazolidin-2-one 

Relevant academic research and scientific papers

Synthesis and application of N-3,5-dinitrobenzoyl and C3 symmetric diastereomeric chiral stationary phases

Three diastereomeric chiral compounds, namely, (R,R)-(+)-2-amino-1,2-diphenylethanol, (1S,2R)-(+)-2-amino-1,2-diphenylethanol, and (1R,2R)-(+)-1,2-diphenylethylenediamine were used as starting materials for preparing three N-3,5-dinitrobenzoyl derivative

Alkene Syn- And Anti-Oxyamination with Malonoyl Peroxides

Malonoyl peroxide 6 is an effective reagent for the syn- or anti-oxyamination of alkenes. Reaction of 6 and an alkene in the presence of O-tert-butyl-N-tosylcarbamate (R3 = CO2 tBu) leads to the anti-oxyaminated product in up to 99% yield. Use of O-methyl-N-tosyl carbamate (R3 = CO2Me) as the nitrogen nucleophile followed by treatment of the product with trifluoroacetic acid leads to the syn-oxyaminated product in up to 77% yield. Mechanisms consistent with the observed selectivities are proposed.

One-pot synthesis of oxazolidinones and five-membered cyclic carbonates from epoxides and chlorosulfonyl isocyanate: Theoretical evidence for an asynchronous concerted pathway

The one-pot reaction of chlorosulfonyl isocyanate (CSI) with epoxides having phenyl, benzyl and fused cyclic alkyl groups in different solvents under mild reaction conditions without additives and catalysts was studied. Oxazolidinones and five-membered cyclic carbonates were obtained in ratios close to 1:1 in the cyclization reactions. The best yields of these compounds were obtained in dichloromethane (DCM). Together with 16 known compounds, two novel oxazolidinone derivatives and two novel cyclic carbonates were synthesized with an efficient and straightforward method. Compared to the existing methods, the synthetic approach presented here provides the following distinct advantageous: being a one-pot reaction with metal-free reagent, having shorter reaction times, good yields and a very simple purification method. Moreover, using the density functional theory (DFT) method at the M06-2X/6-31+G(d,p) level of theory the mechanism of the cycloaddition reactions has been elucidated. The further investigation of the potential energy surfaces associated with two possible channels leading to oxazolidinones and five-membered cyclic carbonates disclosed that the cycloaddition reaction proceeds via an asynchronous concerted mechanism in gas phase and in DCM.

Copper-Catalyzed Enantioselective Reductive Cross-Coupling of Aldehydes and Imines

A copper-catalyzed enantioselective reductive cross-coupling using aromatic aldehydes and imines, producing chiral β-amino alcohols, is described. The catalytic formation of enantioenriched chiral α-alkoxyalkylcopper(I) species from aromatic aldehydes and the subsequent reaction with imine electrophiles are attractive features of this protocol.

Synthesis of new C3 symmetric amino acid- and aminoalcohol-containing chiral stationary phases and application to HPLC enantioseparations

We recently reported a new C3-symmetric (R)-phenylglycinol N-1,3,5-benzenetricarboxylic acid-derived chiral high-performance liquid chromatography (HPLC) stationary phase (CSP 1) that demonstrated better results as compared to a previously described N-3,5-dintrobenzoyl (DNB) (R)-phenylglycinol-derived CSP. Over a decade ago, (S)-leucinol, (R)-phenylglycine, and (S)-leucine derivatives were used as the starting materials of 3,5-DNB-based Pirkle-type CSPs for chiral separation. In this study, three new C3-symmetric CSPs (CSP 2, 3, and 4) were prepared by combining the ideas and results mentioned above. Here we describe the synthetic procedures and applications of the new C3-symmetric CSPs (CSP 2–CSP 4).

Catalytic, enantioselective N-acylation of lactams and thiolactams using amidine-based catalysts

In contrast to alcohols and amines, racemic lactams and thiolactams cannot be resolved directly via enzymatic acylation or classical resolution. Asymmetric N-acylation promoted by amidine-based catalysts, particularly Cl-PIQ 2 and BTM 3, provides a convenient method for the kinetic resolution of these valuable compounds and often achieves excellent levels of enantioselectivity in this process. Density functional theory calculations indicate that the reaction occurs via N-acylation of the lactim tautomer and that cation-π interactions play a key role in the chiral recognition of lactam substrates.

COMPOSITIONS AND METHODS FOR CYCLOFRUCTANS AS SEPARATION AGENTS

The present invention relates to derivatized cyclofructan compounds, compositions comprising derivatized cyclofructan compounds, and methods of using compositions comprising derivatized cyclofructan compounds for chromatographic separations of chemical species, including enantiomers. Said compositions may comprise a solid support and/or polymers comprising derivatized cyclofructan compounds.

Resolution of pentafluorophenyl esters using oxazolidin-2-ones

A series of structurally related racemic pentafluorophenyl active esters were resolved using an equimolar amount of (S)-4-phenyloxazolidin-2-one. The levels of diastereocontrol were found to be excellent (80-96% de) at ～40% conversion.

Bis(o-nitrophenyl) carbonate as a new reagent for the synthesis of chiral oxazolidin-2-ones

Bis(o-nitrophenyl) carbonate reacts under mild conditions with chirals 1,2-amino alcohols and, after addition of DMAP, affords the corresponding oxazolidin-2-ones in very good yields.