32233-40-2Relevant articles and documents
HPLC and SFC enantioseparation of (±)-Corey lactone diol: Impact of the amylose tris-(3,5-dimethylphenylcarbamate) coating amount on chiral preparation
Wang, Huiying,Wang, Qiuhua,Wu, Yaling,Cheng, Lingping,Zhu, Lunan,Zhu, Junchen,Ke, Yanxiong
, p. 855 - 864 (2019)
As an important intermediate of prostaglandins and entecavir, optically pure Corey lactone diol (CLD) has great value in the pharmaceutical industry. In this work, the enantioseparation of (±)-CLD was evaluated using high-performance liquid (HPLC) and supercritical fluid chromatography (SFC). In HPLC, the separations of CLD enantiomers on polysaccharide-based chiral stationary phases with both normal phase and polar organic phase were screened. And the conditions for the enantioseparation were optimized in HPLC and SFC, including the selection of mobile phase, temperature, back-pressure, and other conditions. More important, it was found that the chiral resolutions were greatly enhanced by the increase of the coating amount of ADMPC (amylose tris-(3,5-dimethylphenylcarbamate)) under both HPLC and SFC conditions, which can lead to the increase of the productivity and the decrease of the solvent consumption. The preparations of optically pure CLD were evaluated on a semi-preparative (2?×?25?cm) column packed with 30% ADMPC-coated CSP under HPLC and SFC conditions. Preparative performances in terms of kkd are 1.536?kg racemate/kg CSP/day and 1.248?kg racemate/kg CSP/day in HPLC and SFC, respectively.
A unified strategy to prostaglandins: chemoenzymatic total synthesis of cloprostenol, bimatoprost, PGF2α, fluprostenol, and travoprost guided by biocatalytic retrosynthesis
Chen, Fener,Huang, Zedu,Jiang, Meifen,Li, Weijian,Tang, Pei,Ye, Baijun,Zhang, Guo-Tai,Zhu, Kejie
, p. 10362 - 10370 (2021/08/16)
Development of efficient and stereoselective synthesis of prostaglandins (PGs) is of utmost importance, owing to their valuable medicinal applications and unique chemical structures. We report here a unified synthesis of PGs cloprostenol, bimatoprost, PGF2α, fluprostenol, and travoprost from the readily available dichloro-containing bicyclic ketone6aguided by biocatalytic retrosynthesis, in 11-12 steps with 3.8-8.4% overall yields. An unprecedented Baeyer-Villiger monooxygenase (BVMO)-catalyzed stereoselective oxidation of6a(99% ee), and a ketoreductase (KRED)-catalyzed diastereoselective reduction of enones12(87?:?13 to 99?:?1 dr) were utilized in combination for the first time to set the critical stereochemical configurations under mild conditions. Another key transformation was the copper(ii)-catalyzed regioselectivep-phenylbenzoylation of the secondary alcohol of diol10(9.3?:?1 rr). This study not only provides an alternative route to the highly stereoselective synthesis of PGs, but also showcases the usefulness and great potential of biocatalysis in construction of complex molecules.
Preparation method corey lactone diol
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, (2021/10/11)
The invention provides a preparation method of corey lactone diol, which has the advantages of easily available raw materials. The method has the characteristics of mild reaction conditions, simple operation, simple synthetic route, high chemical yield, low cost and the like, and is suitable for industrial production.
Asymmetric Synthesis of Corey Lactone and Latanoprost
Hayashi, Yujiro,Umekubo, Nariyoshi
supporting information, p. 6221 - 6227 (2020/09/21)
Corey lactone was synthesized in a single pot within 152 minutes in a 50 % overall yield via pot and time economical manner. Latanoprost, an antiglaucoma blockbuster drug, was also synthesized via seven pot reaction with five purifications in a 25 % total yield. One of the key reactions is asymmetric domino Michael/Michael reaction, formal [3+2] cycloaddition reaction, of 3-(dimethylphenylsilyl)propenal and ethyl 4-oxo-2-pentenoate, catalyzed by diphenylprolinol silyl ether, which constructed the core substituted cyclopentanone derivative with nearly optically pure form.
A synthesis method of the branch stands lactone diol
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Paragraph 0085-0088, (2019/06/07)
The invention discloses a method for the branch stands lactone diol (( -) - Corey lactone diol) synthetic method, synthesis method of the invention is to dicyclopentadiene as raw materials, by depolymerization, cyclization, oxidation, dechlorination, open-loop, split, Prins reaction, hydrolysis reaction to obtain the target product. The invention discloses a synthetic route, raw material economic, high separation efficiency, and is suitable for industrial production.
Access to a Key Building Block for the Prostaglandin Family via Stereocontrolled Organocatalytic Baeyer–Villiger Oxidation
Zhu, Kejie,Hu, Sha,Liu, Minjie,Peng, Haihui,Chen, Fen-Er
, p. 9923 - 9927 (2019/05/16)
A new protocol for the construction of a crucial bicyclic lactone of prostaglandins using a stereocontrolled organocatalytic Baeyer–Villiger (B-V) oxidation was developed. The key B-V oxidation of a racemic cyclobutanone derivative with aqueous hydrogen peroxide has enabled an early-stage construction of a bicyclic lactone skeleton in high enantiomeric excess (up to 95 %). The generated bicyclic lactone is fully primed with two desired stereocenters and enabled the synthesis of the entire family of prostaglandins according to Corey′s route. Furthermore, the reactivity and enantioselectivity of B-V oxidation of racemic bicyclic cyclobutanones were evaluated and 90–99 % ee was obtained, representing one of the most efficient routes to chiral lactones. This study further facilitates the synthesis of prostaglandins and chiral lactone-containing natural products to promote drug discovery.
Process for Preparing Lubiprostone and Intermediate Therefor
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Paragraph 0163; 0164, (2017/05/12)
The present invention relates to a method for producing lubiprostone and an intermediate product used therefor. According to the present invention, the selective introduction of a protecting group onto corey lactone diol enables the production of lubiprostone in an efficient and economical way.
Transformation of δ-lactone in γ-lactone in the Corey route for synthesis of prostaglandins
T?nase, Constantin I.,Dr?ghici, Constantin
, p. 845 - 853 (2015/06/30)
(Un)substituted benzoate ester protected δ-lactone alcohols are alcoholized in acid catalysis in almost quantitative yield to hydroxyl-halogenoesters. For alkylesters the yield drops to ～70%. After changing the protection between primary and secondary alcohols, the intermediate halogenoesters are transformed into the known γ-lactone alcohols protected as ether, silyl-ether or trityl at the secondary alcohol group. Unprotected δ-lactone alcohol 1 is also quantitatively transformed in chloroester 20. After selective protection of the primary alcohol with bulky ether groups, this is finally transformed into the known Corey γ-lactone alcohol, protected as ester at the secondary alcohol.
A novel chemoselective cleavage of (tert-butyl)(dimethyl)silyl (TBS) ethers catalyzed by Ce(SO4)2·4 H2O
González-Calderón, Davir,González-González, Carlos A.,Fuentes-Benítez, Aydeé,Cuevas-Yá?ez, Erick,Corona-Becerril, David,González-Romero, Carlos
, p. 965 - 972 (2014/08/05)
(tert-Butyl)(dimethyl)silyl (tBuMe2Si; TBS) phenyl/alkyl ethers were efficiently cleaved to the corresponding parent hydroxy compounds in good yields using catalytic amounts of Ce(SO4) 2·4 H2O by microwave-assisted or conventional heating in MeOH. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl (iPr3Si; TIPS) and (tert-butyl)(diphenyl)silyl ( tBuPh2Si; TBDPS) ethers. Copyright
Aluminium chloride hexahydrate (AlCl3.6H2o): An efficient, facile, mild, and highly chemoselective catalytic deprotection of tert-butyldimethylsilyl (tbs) ethers
Gonzalez-Calderon, Davir,Benitez-Puebla, Luis J.,Gonzalez-Gonzalez, Carlos A.,Garcia-Eleno, Marco A.,Fuentes-Benitez, Aydee,Cuevas-Yanez, Erick,Corona-Becerril, David,Gonzalez-Romero, Carlos
, p. 1258 - 1265 (2014/04/17)
tert-Butyldimethylsilyl (TBS) phenyl / alkyl ethers were cleaved to the corresponding efficiently parent hydroxyl compounds in good yields using catalytic amounts of AlCl3.6H2O by conventional or microwave-assisted heating in methanol or isopropanol solution. Intramolecular and competitive experiments demonstrated the chemoselective deprotection of TBS ethers in the presence of triisopropylsilyl and tert-butyldiphenylsilyl ethers.
