Ring expansions of 1-azabicyclo[n.1.0]alkanes. Recent developments

Tymoshenko, Dmytro O.

doi:10.3998/ark.5550190.0012.105

Cited by 8 publications

(1 citation statement)

References 15 publications

(16 reference statements)

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“…The ring expansion of pyrrolidines to piperidines via an aziridinium intermediate under kinetic and thermodynamic conditions is well-established [23,24,25,26,27,28]. This method was used to access piperidines 30 , 30′ from prolinols 29 , 29′ .…”

Section: From Cyclic Substratesmentioning

confidence: 99%

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Rioton¹,

Pardo²,

Cossy³

2017

Molecules

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A comprehensive survey of pathways leading to the generation of α-trifluoromethyl monocyclic piperidinic derivatives is provided (65 references). These compounds have been synthesized either from 6-membered rings e.g., pipecolic acid or lactam derivatives by introduction a trifluoromethyl group, from pyridine or pyridinone derivatives by reduction, and from 5-membered rings e.g., prolinol derivatives by ring expansion, from linear amines by cyclization or from dienes/dienophiles by [4 + 2]-cycloaddition.

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Section: From Cyclic Substratesmentioning

confidence: 99%

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Rioton¹,

Pardo²,

Cossy³

2017

Molecules

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Bicyclic Aziridinium Ions in Azaheterocyclic Chemistry – Preparation and Synthetic Application of 1‐Azoniabicyclo[n.1.0]alkanes

et al. 2016

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Scheme 4. Possible isomerizations of bicyclic aziridiniumi ntermediates 10. Scheme5.Reactiono f1 -azabicyclo[1.1.0]butane 16 with aromatic thiols and amines. Scheme 10. Solvent-dependent transformation of 2-(bromomethyl)aziridines 35. Scheme 9. Reduction of amines 33 and 39 to aziridines 34 and azetidines 38. Scheme 14. Nucleophile-dependent conversion of mesyloxyazetidine 52. Scheme 15. Ring contraction of 3,3-dichloroazetidines 55 to aziridines 60. Scheme 19. Ring expansion of 2-chloromethyl-a nd 2-(methanesulfonyloxymethyl)azetidines 72 to 3-substituted pyrrolidines 73 and 74. Scheme 20. DAST-promoted ring expansion of 2-(hydroxymethyl)azetidines 76. Scheme 40. Conversion of 1-azabicyclo[4.1.0]heptanes 159 to (thio)morpholines 161 and (thi)azepanes 163.

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Enantioselective Synthesis and Physicochemical Properties of Libraries of 3‐Amino‐ and 3‐Amidofluoropiperidines

Orliac

Routier

Charvillon

et al. 2014

Chemistry A European J

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The enantioselective syntheses of 3-amino-5-fluoropiperidines and 3-amino-5,5-difluoropiperidines were developed using the ring enlargement of prolinols to access libraries of 3-amino- and 3-amidofluoropiperidines. The study of the physicochemical properties revealed that fluorine atom(s) decrease(s) the pKa and modulate(s) the lipophilicity of 3-aminopiperidines. The relative stereochemistry of the fluorine atoms with the amino groups at C3 on the piperidine core has a small effect on the pKa due to conformationnal modifications induced by fluorine atom(s). In the protonated forms, the C-F bond is in an axial position due to a dipole-dipole interaction between the N-H(+) and C-F bonds. Predictions of the physicochemical properties using common software appeared to be limited to determine correct values of pKa and/or differences of pKa between cis- and trans-3-amino-5-fluoropiperidines.

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Ring expansions of 1-azabicyclo[n.1.0]alkanes. Recent developments

Cited by 8 publications

References 15 publications

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Synthesis of Substituted α-Trifluoromethyl Piperidinic Derivatives

Bicyclic Aziridinium Ions in Azaheterocyclic Chemistry – Preparation and Synthetic Application of 1‐Azoniabicyclo[n.1.0]alkanes

Enantioselective Synthesis and Physicochemical Properties of Libraries of 3‐Amino‐ and 3‐Amidofluoropiperidines

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