Asymmetric Hydrolysis of (±)-1,2-Diacetoxy-3-chloropropane and Its Related Compounds with Lipase. Synthesis of Optically Pure (<i>S</i>)-Propranolol

Iriuchijima, Shinobu; Kojima, Natsuko

doi:10.1080/00021369.1982.10865218

Cited by 4 publications

(2 citation statements)

References 4 publications

(8 reference statements)

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“…Hydrolysis of 1,2-diacetoxy-3-chloropropane (12) Fig. (5) by more than 10 commercially available lipases was reported by Iriuchijima [36]. The lipoprotein lipase from Pseudomonas aeruginosa showed a very good specificity toward (R)-isomer 13, leaving the (S)-12 with the optical purity 90%.…”

Section: B Diolsmentioning

confidence: 93%

Biocatalytic Approaches to Optically Active β-Blockers

Żelaszczyk¹,

Kieć‐Kononowicz

2007

CMC

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Beta-blockers are a very important group of drugs widely used for the treatment of cardiovascular diseases. All aryloxyaminopropanols are chiral and show different stereoselectivity in their pharmacodynamic and pharmacokinetic properties for each enantiomer. The more potent beta-adrenoceptor blocking activity is generally associated with (S)-enantiomers. Most beta-blocking agents are sold as racemates although (R)-enantiomers not only show in some cases lack of activity but might be responsible for undesirable effects. Among reports on the direct enzymatic resolution of the most representative beta-blocker propranolol, the most interesting is N-acetylation method with commercially available lipases to yield (S)-N-acetylpropranolol. Another type of the one-step (S)-isomer biocatalytic preparation from racemic mixture of propranolol is the biodegradation with the fungus. Biocatalytic methods of obtaining homochiral beta-blockers that are focused on production of versatile precursors are widely described in literature. The strategies based on the use of glycidol and derivatives as C-3 synthones have been shown to be extremely useful for the introduction of the 2-propanol chain on the aromatic system. Halohydrins are the established intermediates in the preparation of optically active beta-blockers. Its resolution by esterhydrolases has been used as a standard alternative in preparation of the homochiral propranolol. Additionally, the enzymatic resolution of the following intermediates was reported: 1-azido-3-aryloxy-2-propanols, 4-(1-aryloxy)-3-hydroxybutyric acid esters, glycerol and cyanohydrin derivatives. However, even the highly enantioselective lipase-catalyzed process can only provide 50% of the starting racemate in an optically active form. An alternative method such as a reduction of a prochiral ketone by various strains of yeast might quantitatively provide an enantiomeric product with a yield greater than 50%. The reported substrates for microbial reductions were: 1-halo-aryloxypropan-2-ones and 1-acetoxy-aryloxypropan-2-ones.

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Section: B Diolsmentioning

confidence: 93%

Biocatalytic Approaches to Optically Active β-Blockers

Żelaszczyk¹,

Kieć‐Kononowicz

2007

CMC

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“…Chemical synthesis of optically active MCH from D-mannitol (Porter and Jones 1982), methyl-6-chloro-6-deoxy-oz-D-gluCorrespondence to: T. Suzuki copyranoside and methyl-5-chloro-5-deoxy-a-L-arabinofuranoside (Jones 1978) have been reported. On the other hand, with respect to microbial and enzymatic preparations of optically active MCH, several methods are known (Iriuchijima and Kojima 1982;Ladner and Whitesides 1984;Takahashi et al 1989;Nakamura et al 1991). For mass production of optically active MCH and GLD, the microbial and enzymatic methods are considered to be simpler, more effective and more practical than the chemical methods.…”

Section: Introductionmentioning

confidence: 99%

Production of highly optically active (R)-3-chloro-1,2-propanediol using a bacterium assimilating the (S)-isomer

Suzuki

Kasai

Yamamoto

et al. 1993

Appl Microbiol Biotechnol

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A bacterium that assimilates (S)-3-chloro-1,2-propanediol [monochlorohydrin (MCH)] was isolated from soil by enrichment culture. The bacterium was identified as Pseudomonas sp. by taxonomic studies. The strain grew in a medium c~ontaining racemic MCH as a source of carbon and degraded (S)-MCH stereoseIectively, liberating chloride ions. The residual isomer was the (R)-form [99.5% enantiomeric excess (ee)], which was obtained from the racemate in a final yield of 36% by using this strain. Subsequently, highly optically active (R)-glycidol (GLD) (99.3% e e ) w a s prepared from the (R)-MCH obtained by reaction in alkaline solution. The cell-free extracts of the cells had both dehalogenating and epoxide-opening activities, which converted various halohydrins to the corresponding epoxides and epoxides to the corresponding diols, respectively.

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Regioselective Synthesis of 1,N²-Etheno-2‘-Deoxyguanosine and Its Generation in Oligomeric DNA

Huang

Torres

Iden

et al. 2003

Chem. Res. Toxicol.

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Chloroethylene oxide and chloroacetaldehyde, reactive intermediates derived from vinyl chloride, and the epoxy-hydroxy-alkanals, produced endogenously in the metabolism of polyunsaturated fatty acids, react with nucleic acid bases in DNA to form exocyclic etheno derivatives of 2'-deoxyadenosine, 2'-deoxyguanosine, and 2'-deoxycytidine. This paper describes an efficient method for the synthesis of the exocyclic 1,N(2)-etheno adduct of 2'-deoxyguanosine and its incorporation into DNA oligomers using automated synthesis techniques. The synthesis was initiated by a high-yield alkylation of N(2)-protected 2'-deoxyguanosine at the 1-position with 1,2-diacetoxy-3-bromopropane. The product was converted to the 5'-O-dimethoxytrityl-3'-O-phosphoramidite using published techniques and incorporated site specifically into DNA oligomers with 99% coupling efficiency. Ring closure to yield the 6-hydroxyethano derivative was accomplished by oxidation with sodium periodate, and facile dehydration then afforded DNA oligomers containing 1,N(2)-etheno-2'-deoxyguanosine. All oligomers were characterized fully by physicochemical methods.

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Asymmetric Hydrolysis of (±)-1,2-Diacetoxy-3-chloropropane and Its Related Compounds with Lipase. Synthesis of Optically Pure (S)-Propranolol

Cited by 4 publications

References 4 publications

Biocatalytic Approaches to Optically Active β-Blockers

Biocatalytic Approaches to Optically Active β-Blockers

Production of highly optically active (R)-3-chloro-1,2-propanediol using a bacterium assimilating the (S)-isomer

Regioselective Synthesis of 1,N²-Etheno-2‘-Deoxyguanosine and Its Generation in Oligomeric DNA

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Asymmetric Hydrolysis of (±)-1,2-Diacetoxy-3-chloropropane and Its Related Compounds with Lipase. Synthesis of Optically Pure (S)-Propranolol

Cited by 4 publications

References 4 publications

Biocatalytic Approaches to Optically Active &#946;-Blockers

Biocatalytic Approaches to Optically Active &#946;-Blockers

Production of highly optically active (R)-3-chloro-1,2-propanediol using a bacterium assimilating the (S)-isomer

Regioselective Synthesis of 1,N2-Etheno-2‘-Deoxyguanosine and Its Generation in Oligomeric DNA

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Biocatalytic Approaches to Optically Active β-Blockers

Biocatalytic Approaches to Optically Active β-Blockers

Regioselective Synthesis of 1,N²-Etheno-2‘-Deoxyguanosine and Its Generation in Oligomeric DNA