86040-07-5Relevant academic research and scientific papers
First Synthesis and Characterization of Stereoisomers of Choleretic Drug Dihydroxydibutylether
Yue, Qiming,Zhao, Yi,Sun, Baohou,Hai, Li,Guo, Li,Wu, Yong
, p. 1145 - 1152 (2015/11/02)
Dihydroxydibutylether (DHBE) is a choleretic drug used for the treatment of gallstone and hepatic disorders due to its choleretic activity and hepatoprotective action. The drug is a mixture of three regioisomers. The main regioisomer 3-(3-hydroxylbutoxy)-
First Stereoselective Synthesis of the Cytotoxic Polyketide (4R)-1-(3,5-Dihydroxyphenyl)-4-hydroxypentan-2-one
Rajendra Prasad, Kothakonda,Purushotham Reddy, Sudina,Suresh Babu, Katragadda,Madhusudana Rao, Janaswamy
, p. 143 - 147 (2015/10/19)
The first stereoselective synthesis of the cytotoxic polyketide (4R)-1-(3,5-dihydroxyphenyl)-4-hydroxypentan-2-one (1) was achieved from readily available propylene oxide and 3,5-dimethoxybenzyl alcohol. The synthesis involves Jacobsen's hydrolytic kinetic resolution (HKR) and Grignard reaction as key steps.
Intramolecular OH...Fluorine Hydrogen Bonding in Saturated, Acyclic Fluorohydrins: The γ-Fluoropropanol Motif
Linclau, Bruno,Peron, Florent,Bogdan, Elena,Wells, Neil,Wang, Zhong,Compain, Guillaume,Fontenelle, Clement Q.,Galland, Nicolas,Le Questel, Jean-Yves,Graton, Jér?me
, p. 17808 - 17816 (2015/12/08)
Fluorination is commonly exercised in compound property optimization. However, the influence of fluorination on hydrogen-bond (HB) properties of adjacent functional groups, as well as the HB-accepting capacity of fluorine itself, is still not completely understood. Although the formation of OH...F intramolecular HBs (IMHBs) has been established for conformationally restricted fluorohydrins, such interaction in flexible compounds remained questionable. Herein is demonstrated for the first time - and in contrast to earlier reports - the occurrence of OH...F IMHBs in acyclic saturated γ-fluorohydrins, even for the parent 3-fluoropropan-1-ol. The relative stereochemistry is shown to have a crucial influence on the corresponding h1JOH...F values, as illustrated by syn- and anti-4-fluoropentan-2-ol (6.6 and 1.9 Hz). The magnitude of OH...F IMHBs and their strong dependence on the overall molecular conformational profile, fluorination motif, and alkyl substitution level, is rationalized by quantum chemical calculations. For a given alkyl chain, the "rule of shielding" applies to OH...F IMHB energies. Surprisingly, the predicted OH...F IMHB energies are only moderately weaker than these of the corresponding OH...OMe. These results provide new insights of the impact of fluorination of aliphatic alcohols, with attractive perspectives for rational drug design.
Total synthesis of sedum alkaloids via catalyst controlled aza-cope rearrangement and hydroformylation with formaldehyde
Ren, Hong,Wulff, William D.
, p. 242 - 245 (2013/03/28)
The catalytic asymmetric aminoallylation of chiral aldehydes is developed as a new method for the catalyst controlled synthesis of syn-and anti-1,3-aminoalcohols. This methodology is highlighted in the synthesis of the sedum alkaloids (+)-sedridine and (+)-allosedridine both of which have their final carbon incorporated during closure of the piperidine ring via a hydroformylation with formaldehyde.
Palladium-catalyzed selective anti-markovnikov oxidation of allylic esters
Dong, Jia Jia,Fananas-Mastral, Martin,Alsters, Paul L.,Browne, Wesley R.,Feringa, Ben L.
, p. 5561 - 5565 (2013/06/27)
An aldol alternative: The palladium(II)-catalyzed anti-Markovnikov oxidation of allylic esters to aldehydes at room temperature provides a viable alternative to valuable cross aldol products. High regioselectivity towards the aldehyde product was achieved using the ester protecting group for the allylic alcohol. Rapid isomerization and the much higher rate of oxidation of the branched isomer result in the same product forming from both linear and branched allylic esters. Copyright
Lewis acid-promoted addition of 1,3-bis(silyl)propenes to aldehydes: A route to 1,3-dienes
Borg, Tessie,Tuzina, Pavel,Somfai, Peter
, p. 8070 - 8075 (2011/11/28)
The Lewis acid-promoted addition of 1,3-bis(silyl)-propenes to aldehydes to provide the corresponding (E)-1,3-dienes in excellent stereoselectivity and good to excellent yields is reported. The procedure is mild, base-free, and operationally straightforward.
Effective 1,5-, 1,6- and 1,7-remote stereocontrol in reactions of alkoxy- and hydroxy-substituted allylstannanes with aldehydes
Carey, John S.,MacCormick, Somhairle,Stanway, Steven J.,Teerawutgulrag, Aphiwat,Thomas, Eric J.
supporting information; experimental part, p. 3896 - 3919 (2011/06/26)
Alk-2-enylstannanes with 4-, 5- and 6-alkoxy- or -hydroxy-substituents are transmetallated stereoselectively with tin(iv) halides to generate allyltin trihalides which react with aldehydes to give (Z)-alk-3-enols with useful levels of 1,5-, 1,6- and 1,7-stereocontrol. Alk-2-enylstannanes with a stereogenic centre bearing a hydroxy or alkoxy group at the 4-, 5- or 6-position, react with overall (Z)-1,5-, 1,6- and 1,7-syn-stereoselectivity with respect to the hydroxy and alkoxy substituents. The analogous reactions of alkoxy- and -hydroxyalk-2-enylstannanes with a methyl bearing stereogenic centre at the 4- or 5-position react with overall (Z)-1,5- and 1,6-anti-stereoselectivity with respect to the hydroxy and methyl substituents.
Synthesis of chiral 4-hydroxy-2,3-unsaturated carbonyl compounds from 3,4-epoxy alcohols by oxidation: Application in the formal synthesis of macrosphelide A
Chakraborty, Tushar K.,Purkait, Subhas,Das, Sanjib
, p. 9127 - 9135 (2007/10/03)
An interesting transformation during the oxidation of 3,4-epoxy alcohols 1a-d, derived from the corresponding homoallylic alcohols, led to the formation of 4-hydroxy-2,3-unsaturated carbonyls 2a-d in very good yields. One of these products 2c was transfor
Lipase mediated resolution of 1,3-butanediol derivatives: Chiral building blocks for pheromone enantiosynthesis. Part 3
Izquierdo, Isidoro,Plaza, Maria T.,Rodriguez, Miguel,Tamayo, Juan A.,Martos, Alicia
, p. 293 - 300 (2007/10/03)
(R,S)-1,3-Butanediol 5 was kinetically resolved by enzymatic acetylation with vinyl acetate under the presence of Chirazyme L-2, c-f, yielding (S)-1-O-acetyl-1,3-hydroxybutane 6 and (R)-1,3-di-O-acetyl-1,3-butanediol 7 with enantiomeric excesses of 91% (E = 67.3). Compounds 6 and 7 were easily transformed into the corresponding (S)-3-O-(2-methoxyethoxymethyl)-3-hydroxybutanal 10 and (R)-3-benzyloxybutanal 19, through a protection-deprotection and functional group interchange methodology. Subsequent reaction of 10 and 19 with 3-(methoxycarbonylpropionylmethylene)triphenylphosphorane afforded methyl (E,S)-8-O-(2-methoxyethoxymethyl)-4-oxo-5-nonenoate 12 and (E,R)-8-benzyloxy-4-oxo-5-nonenoate 20. The alkenes 19 and 20 were then catalytically hydrogenated to the corresponding saturated esters 13 and 21. Treatment of 13 and 21 with 1,2-ethanedithiol/F3B·OEt2 afforded dithioketals 14 and 22, which were respectively reduced to (S)-1,8-dihydroxy-4-nonanone ethylidenedithioketal 15 and (R)-8-O-benzyl-1,8-dihydroxy-4-nonanone ethylidenedithioketal 23. Finally, deprotection of 15 by catalytic hydrogenation under acidic conditions gave the expected (5S,7S)-(-)-7-methyl-1,6-dioxaspiro[4.5]decane 1. The (5R,7R)-(+)-1 enantiomer was analogously prepared from 23. Both compounds were formed by this procedure with an e.e. of 91%.
Syntheses of β-resorcylic acid derivatives, novel potato micro-tuber inducing substances isolated from Lasiodiplodia theobromae
Yang,Toshima,Yoshihara
, p. 5377 - 5384 (2007/10/03)
The syntheses of β-resorcylic acid derivatives 1 and 2, isolated from fungus Lasiodiplodia theobromae, and their dimethyl ethers were accomplished. (R)-(-)-1,3-Butanediol was used as a chiral source of the side chain C6-synthon. The dianion of the benzoic acid moiety was alkylated with C6-bromide to give the desired skeleton. Several β-resorcylic acid derivatives including 1 and 2 were synthesized via hydrogenation, lactonization, demethylation and esterification. The (R)-configuration of the stereogenic center in the side chain was proved by this synthesis. It is confirmed that two phenolic hydroxy groups are required for 1 and 2 to exhibit potato micro-tuber inducing activity.
