77943-39-6 Usage
Description
(4R,5S)-(+)-4-METHYL-5-PHENYL-2-OXAZOLIDINONE is a white to light yellow crystalline powder that is known for its effective chiral auxiliary properties in chemical synthesis. It is particularly useful in the asymmetric synthesis of complex organic compounds, such as (-)-aplysillamide B.
Uses
Used in Pharmaceutical Industry:
(4R,5S)-(+)-4-METHYL-5-PHENYL-2-OXAZOLIDINONE is used as an effective chiral auxiliary for the conjugate addition asymmetric synthesis of (-)-aplysillamide B, a complex organic compound with potential pharmaceutical applications.
Used in Chemical Synthesis:
(4R,5S)-(+)-4-METHYL-5-PHENYL-2-OXAZOLIDINONE is used as a chiral auxiliary in the preparation of N-sulfinyloxazolidinone reagent, a chiral sulfinyl transfer reagent. This reagent reacts with nucleophiles such as Grignard reagents, enolates, and metalated amides to produce chiral sulfoxides, sulfinate esters, and sulfonamides, which are important intermediates in the synthesis of various organic compounds.
Used in Research and Development:
Evan's chiral auxiliary (4R,5S)-(+)-4-METHYL-5-PHENYL-2-OXAZOLIDINONE is also used in research and development for the synthesis of various organic compounds, particularly those requiring chiral centers. It reacts with carboxylic acids to produce corresponding acyl derivatives in the presence of a diisopropylcarbodiimide reagent, facilitating the synthesis of a wide range of chiral compounds.
Preparation
To a solution of (1S,2R)-norephedrine (40 g, 0.26 mol) in toluene (400 mL) was added diethyl carbonate (37 mL, 0.32 mol). The mixture was heated to reflux (under Ar) while 40 mL of solvent was removed through the use of a Dean–Stark apparatus. The mixture was allowed to cool for 20 min, and then sodium methoxide (1 g) was added. Upon reheating, an EtOH/toluene azeotropic mixture was removed at 75–77 °C. After 3 h, the reaction was complete and the temperature of the mixture had increased to 125 °C. The mixture was left to stand at room temperature for 16 h, whereupon (4R,5S)-4-methyl-5-phenyloxazolidin-2-one (40.6 g) crystallized and could be collected. The solvent was removed from the filtrate in vacuo and the residue was redissolved in EtOAc (250 mL). This solution was washed with brine (50 mL) and a precipitate was removed by filtration. The solvent was then removed in vacuo and toluene (50 mL) was added to the residue. Removal of the toluene by distillation yielded oily crystals of the oxazolidinone, which were washed with Et2O to afford 4.5 g (total 45 g, 97%).
Preparation
A mechanically stirred mixture of (1S,2R)-norephedrine 710 (151 g, 1.00 mol) ([α]589 =+ 33.4 (c= 7, water)), as the hydrochloride salt, diphenyl carbonate (236 g, 1.10 mol), and anhydrous potassium carbonate (152 g, 1.10 mol) was heated at 110 °C for 4–6 h. The resultant mixture was then cooled to <60 °C. Excess diphenyl carbonate was hydrolyzed by adding methanol (600 mL) and heating the mixture under reflux for 0.5 h. Sufficient water (400–600 mL) was then added to dissolve the potassium carbonate. Methanol was removed in vacuo. The product and phenol were extracted into dichloromethane (3 × 1 L). The combined extracts were washed with 2 m aqueous sodium hydroxide (3 × 1 L) to remove the phenol, 1 m aqueous hydrochloric acid (1 × 1 L), and brine, dried over anhydrous magnesium sulfate, and concentrated in vacuo to give 195 g (110% mass balance) of a light-yellow solid. Recrystallization from toluene (600 mL) afforded 145–165 g (82–93%) of oxazolidinone 711 as a white crystalline solid.
Check Digit Verification of cas no
The CAS Registry Mumber 77943-39-6 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 7,7,9,4 and 3 respectively; the second part has 2 digits, 3 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 77943-39:
(7*7)+(6*7)+(5*9)+(4*4)+(3*3)+(2*3)+(1*9)=176
176 % 10 = 6
So 77943-39-6 is a valid CAS Registry Number.
InChI:InChI=1/C10H11NO2/c1-7-9(13-10(12)11-7)8-5-3-2-4-6-8/h2-7,9H,1H3,(H,11,12)/t7-,9-/m1/s1
77943-39-6Relevant articles and documents
Asymmetric ammonium ylid rearrangements: the effect of nitrogen asymmetry
Sweeney,Tavassoli, Ali,Workman, James A.
, p. 11506 - 11512 (2006)
[2,3]-Sigmatropic rearrangements of allylic ammonium ylids derived from glycinoylcamphorsultams are highly selective in terms of relative and absolute stereocontrol only when acyclic alkenes are present. When chiral esters of ylids derived from N-methyltetrahydropyridine ('NMTP') undergo rearrangement, the reactions show exclusive cis-stereoselectivity but the products are obtained with virtually no absolute stereocontrol. These observations support the notion that sigmatropic rearrangements of N-chiral ammonium ylids are controlled by nitrogen stereogenicity.
Stereoselective synthesis of oxazolidin-2-ones via an asymmetric aldol/curtius reaction: Concise total synthesis of (?)-cytoxazone
Choi, Hosam,Choi, Joohee,Jang, Hanho,Lee, Kiyoun
, (2021/06/14)
Herein, we are reporting an efficient approach toward the synthesis of 4,5-disubstituted oxazolidin-2-one scaffolds. The developed approach is based on a combination of an asymmetric aldol and a modified Curtius protocol, which uses an effective intramolecular ring closure to rapidly access a range of oxazolidin-2-one building blocks. This strategy also permits a straightforward and concise asymmetric total synthesis of (?)-cytoxazone. Consisting of three steps, this is one of the shortest syntheses reported to date. Ultimately, this convenient platform would provide a promising method for the early phases of drug discovery.
A new type of L-Tertiary leucine-derived ligand: Synthesis and application in Cu(II)-catalyzed asymmetric Henry reactions
Cai, Zedong,Lan, Ting,Ma, Pengfei,Zhang, Jingfang,Yang, Qingqing,He, Wei
, (2019/08/08)
A new series of Schiff bases derived from amino acids were developed as chiral ligands for Cu(II)-catalyzed asymmetric Henry reactions. The optimum ligand 7d exhibited outstanding catalytic efficiency in the Cu(II)-catalyzed asymmetric Henry additions of four nitroalkanes to different kinds of aldehydes to produce 76 desired adducts in high yields (up to 96%) with excellent enantioselectivities, up to 99% enantiomeric excess (ee).
