Lipase kinetic enantiomeric resolution of 1-heteroarylethanols

Kucher, Olexandr V.; Kolodyazhnaya, A. O.; Смолий, О. Б.; Nazarenko, Nadiya K.; Kubyshkin, Vladimir; Mykhailiuk, Pavel K.; Tolmachev, Andrey A.

doi:10.1016/j.tetasy.2016.02.012

Cited by 9 publications

(3 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[27][28][29][30][31][32][33][34][35][36] Of these, acylation using vinyl acetate under lipase catalysis is a well-recognized method for kinetic resolution of meso or racemic diols. 32,33 While secondary alcohols undergo acylation with better selectivity, [37][38][39][40][41][42][43][44][45][46][47] primary -OHs are generally less discriminated by lipases unless in the vicinity of sterically demanding groups. 32,33 While secondary alcohols undergo acylation with better selectivity, [37][38][39][40][41][42][43][44][45][46][47] primary -OHs are generally less discriminated by lipases unless in the vicinity of sterically demanding groups.…”

Section: Introductionmentioning

confidence: 99%

“…[32][33][34] Representative examples of lipases used for acyl transfer are lipase from P. cepacia (Amano PS), lipase-B from Candida antarctica (CAL-B), Candida rugosa (CRL), and P. fluorescens (PFL). 32,33 While secondary alcohols undergo acylation with better selectivity, [37][38][39][40][41][42][43][44][45][46][47] primary -OHs are generally less discriminated by lipases unless in the vicinity of sterically demanding groups. [48][49][50][51][52][53][54][55][56][57][58][59] Several strategies have been attempted to overcome this, such as the use of chiral or sterically demanding acyl donors, 56,60 optimization of solvation conditions, 61 or through sequential resolutions.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

Reddy

Manheri

2019

Chirality

View full text Add to dashboard Cite

Lipase-catalysed enantioselective acetylation and deacetylation routes were investigated to prepare 1,5,6-trisubstituted 7-oxabicyclo[2.2.1]hept-2-ene skeleton in enantio-pure form. The racemic alcohol (6) used in acetylation reaction was accessed through Diels-Alder reaction of TBDMS-protected furfuryl alcohol with maleic anhydride, followed by reduction-benzylation-desilylation sequence. After systematic screening of lipases and solvents, Candida antarctica B on acrylic resin in pentane was identified as the best system that gave >98% ee towards the (+) acetate with 40% conversion, in 30 minutes. Absolute stereochemistry of this product was confirmed by X-ray diffraction analysis of its 3,5-dinitrobenzoate derivative (9). Enantioselective deacetylation of the racemic acetate of this starting material was then studied with the same set of lipases. After various optimization studies, Candida antarctica B in toluene as the solvent was found to be the most effective that gave 49% conversion with >99% ee towards the (+)-alcohol (8) at the end of 18 hours.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

Reddy

Manheri

2019

Chirality

View full text Add to dashboard Cite

show abstract

“…Hydrolytic kinetic resolution of non-chiral epoxides and asymmetric addition of aryl nucleophiles to aldehydes are other common ways to prepare them. Chiral chromatography and kinetic resolution of racemic alcohols, − likely the techniques most frequently used by medicinal chemists, discard half of the racemic materials. Therefore, enantioselective methods, such as Corey–Itsuno reduction , and metal-mediated asymmetric (transfer) hydrogenation of heteroaryl ketones, , represent better approaches, although they are sometimes problematic when applied to heteroaromatic ketones due to the chelating effect .…”

mentioning

confidence: 99%

Enantioselective Bioreduction of Medicinally Relevant Nitrogen-Heteroaromatic Ketones

Bai

Estrada

Gartman

et al. 2023

ACS Med. Chem. Lett.

View full text Add to dashboard Cite

We herein report an enantioselective bioreduction of ketones that bear the most frequently used nitrogenheteroaromatics in FDA-approved drugs. Ten varieties of these nitrogen-containing heterocycles were systematically investigated. Eight categories were studied for the first time and seven types were tolerated, significantly expanding the substrate scope of plantmediated reduction. By use of purple carrots in buffered aqueous media with a simplified reaction setup, this biocatalytic transformation was achieved within 48 h at ambient temperature, offering medicinal chemists a pragmatic and scalable tool to access a broad variety of nitrogen-heteroaryl-containing chiral alcohols. With multiple reactive sites, the structurally diverse set of chiral alcohols can be used for library compound preparation, early routescouting activities, and synthesis of other pharmaceutical molecules, favorably accelerating medicinal chemistry campaigns.

show abstract

One‐Pot Three‐Component Synthesis of Alkylthio‐/Arylthio‐ Substituted Imidazo[1,2‐a]pyridine Derivatives via C(sp²)–H Functionalization

et al. 2017

View full text Add to dashboard Cite

Sulfenylation is an important transformation to generate C−S bonds in organic synthesis. Here, two three‐component synthetic protocols have been developed by using imidazo[1,2‐a]pyridine, inorganic, odorless S8 and alcohols or arylboronic acids as reactants to make alkylthio‐/arylthio‐substituted imidazo[1,2‐a]pyridine derivatives via C(sp2)–H functionalization. The reactions proceeded with high efficiency and broad functional group tolerance, affording the products regioselectively and in good yields.magnified image

show abstract

Lipase kinetic enantiomeric resolution of 1-heteroarylethanols

Cited by 9 publications

References 38 publications

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

Enantioselective Bioreduction of Medicinally Relevant Nitrogen-Heteroaromatic Ketones

One‐Pot Three‐Component Synthesis of Alkylthio‐/Arylthio‐ Substituted Imidazo[1,2‐a]pyridine Derivatives via C(sp²)–H Functionalization

Contact Info

Product

Resources

About

Lipase kinetic enantiomeric resolution of 1-heteroarylethanols

Cited by 9 publications

References 38 publications

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution

Enantioselective Bioreduction of Medicinally Relevant Nitrogen-Heteroaromatic Ketones

One‐Pot Three‐Component Synthesis of Alkylthio‐/Arylthio‐ Substituted Imidazo[1,2‐a]pyridine Derivatives via C(sp2)–H Functionalization

Contact Info

Product

Resources

About

One‐Pot Three‐Component Synthesis of Alkylthio‐/Arylthio‐ Substituted Imidazo[1,2‐a]pyridine Derivatives via C(sp²)–H Functionalization