Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocycloalkanols

Kolodiazhna, Olga O.; Kolodiazhna, Anastasy O.; Kolodiazhnyi, Oleg I.

doi:10.1016/j.tetasy.2012.11.011

Cited by 18 publications

(12 citation statements)

References 35 publications

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“…In the other cases, chemical correlation was performed, as illustrated in Scheme , by the attempted formation of epoxides from the halohydrins . The minor syn -isomer, as illustrated for syn - 9a , has the appropriate orientation of the oxygen atom and the halogen atom to cyclize, whereas the isomer anti - 9a does not. − When mixtures of stereoisomers were subjected to these conditions, as illustrated for anti - 9b , only the syn -stereoisomer underwent cyclization. The stereochemical configurations of alcohols anti- 6a , b , anti- 8a , b , and anti- 9b were assigned based upon the fact that they did not undergo even a trace of cyclization even after extended periods of time.…”

Section: Resultsmentioning

confidence: 99%

Diastereoselective Additions of Allylmagnesium Reagents to α-Substituted Ketones When Stereochemical Models Cannot Be Used

et al. 2021

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The stereoselectivities of reactions of allylmagnesium reagents with chiral ketones cannot be easily explained by stereochemical models. Competition experiments indicate that the complexation step is not reversible, so nucleophiles cannot access the widest range of possible encounter complexes and therefore cannot be analyzed easily using available models. Nevertheless, additions of allylmagnesium reagents to a ketone can still be stereoselective provided that the carbonyl group adopts a conformation that leads to one face being completely blocked from the approach of the allylmagnesium reagent.

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Section: Resultsmentioning

confidence: 99%

Diastereoselective Additions of Allylmagnesium Reagents to α-Substituted Ketones When Stereochemical Models Cannot Be Used

et al. 2021

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“…trans-2-Fluorocycloalkanols 88 (n = 1, 2) were used to prepare other building blocks via the common functional group transformations, e. g. α-fluoroketones 89, [89][90][91] cis-2-fluorocycloalkanols 90, [89,91,92] cis-2-fluorocycloalkylamines 91, [89,93] or cis-2-fluorocycloalkylhydrazines 92 [94] (Scheme 31).…”

Section: Synthesis Of β-Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

“…For both cis-and trans-2-fluorocyclopentanols (91 a and 88 a, respectively), efficient enzymatic resolution methods were developed, allowing for the preparation of both enantiomers with 96-99 % ee on gram scale. [86,89,91] Some efforts were also put into development of asymmetric ring opening in oxiranes 87 with fluoride. [95] In particular, Haufe and co-workers used chiral salen complex 93 (0.5-1 eq) with AgFÀ Bu 4 N + H 2 F 3 as the fluorinating agent in acetonitrile (Figure 3).…”

Section: Synthesis Of β-Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

“…[158] Also, diastereoselective fluorination of enamide 111 was reported (Scheme 36). [159] Further transformations of α-fluorinated ketones 108 for the synthesis of monofluorinated building blocks included reduction to alcohols of type 90 (see Scheme 31) [89,91,92] and reductive aminations. In particular, highly diastereoselective reduction of imines 112 with triethylsilane was described by Davis and coauthors (Scheme 37).…”

Section: Synthesis Of β-Fluorinated Cycloalkyl Building Blocksmentioning

confidence: 99%

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Fluorinated Cycloalkyl Building Blocks for Drug Discovery

et al. 2022

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The review covers various aspects of fluorinated cycloalkyl (C3−C7) building blocks for drug discovery, including their synthesis, key physicochemical properties, and biological and medicinal applications of their derivatives. The discussed synthetic methods include classical nucleophilic fluorinations of various substrates, the addition of fluorine and another heteroatom to double bonds, cycloadditions and other transformations of fluorine‐containing substrates, as well as some newer reactions like fluorination of non‐activated and remotely activated C−H bonds, decarboxylative and deborylative fluorinations, etc. The known data on the effect of introducing the fluorinated cycloalkyl groups on the compound's key in vitro parameters (such as acidity/basicity, lipophilicity, conformational behavior, and short contact capabilities) are surveyed. Finally, applications of fluorinated cycloalkyl building block derivatives in the design of biologically active compounds (including marketed drugs Maraviroc, Ivosidenib, and Sitafloxacin) are covered, with a focus on the fluorination impact.

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“…b) Cis-2-Fluorocyclopentanol was prepared from the fluorocyclopentanone 7 (1.1 g, 10 mmol) in 50 mL of methanol and sodium borohydride (3.5, 0.1 mol) at 0 °C according to general methodology earlier described by us. 12 Yield 50%, bp 55 °C (15mm Hg). Lit.…”

Section: Trans-2-fluorocyclopentan-1-ol [(+/-)-6mentioning

confidence: 99%

Synthesis of optically active vicinal fluorocyclopentanols and fluorocyclopentanamines by enzymatic deracemization

Kolodiazhna¹,

Prysiazhnuk²,

Kolodiazhna³

et al. 2021

Arkivoc

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All possible stereoisomers of cis-and trans-2-fluorocyclopentan-1-ols were obtained by kinetically controlled deracemization in the presence of lipases in organic media. High enantioselectivities and good yields of stereomers were obtained for all substrates. Optically pure 1,2-fluorocyclopentan-1-ols were converted to 2fluoro-cyclopentan-1-amines using the Mitsunobu reaction. The absolute configurations were determined using the Kazlauskas rule and chemical correlation. The interaction of substrates with enzymes has considered using Koshland induced fit theory.

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Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocycloalkanols

Cited by 18 publications

References 35 publications

Diastereoselective Additions of Allylmagnesium Reagents to α-Substituted Ketones When Stereochemical Models Cannot Be Used

Diastereoselective Additions of Allylmagnesium Reagents to α-Substituted Ketones When Stereochemical Models Cannot Be Used

Fluorinated Cycloalkyl Building Blocks for Drug Discovery

Synthesis of optically active vicinal fluorocyclopentanols and fluorocyclopentanamines by enzymatic deracemization

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