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Beilstein J. Org. Chem. 2017, 13, 2316–2325, doi:10.3762/bjoc.13.228
Graphical Abstract
Figure 1: Examples of conformationally biased amino acids [1-10]. Compound 6 is a target of this work.
Scheme 1: The first synthetic approach.
Scheme 2: The second synthetic approach.
Scheme 3: The third synthetic approach.
Scheme 4: The fourth synthetic approach (partially reproduced from ref. [17]).
Figure 2: Selected J values and the inferred molecular conformations of 6a and 6b.
Beilstein J. Org. Chem. 2013, 9, 2696–2708, doi:10.3762/bjoc.9.306
Figure 1: Fluorination alters the reactivity of aziridines.
Scheme 1: Fluorination makes β-lactam derivatives more reactive towards lipase-catalysed methanolysis.
Figure 2: The ring pucker in azetidine derivatives can be influenced by a C–F…N+ charge–dipole interaction.
Figure 3: Fluorination ridifies the pyrrolidine rings of ligand 10, with several consequences for its G-quadr...
Figure 4: Proline 11 readily undergoes a ring-flip process, but (4R)-fluoroproline 12 is more rigid because o...
Scheme 2: Hyperconjugation rigidifies the ring pucker of a fluorinated organocatalyst 14, leading to higher e...
Figure 5: Fluorinated piperidines prefer the axial conformation, due to stabilising C–F…N+ interactions.
Figure 6: Fluorination can rigidify a substituted azepane, but only if it acts in synergy with the other subs...
Figure 7: The eight-membered N-heterocycle 24 prefers an axial orientation of the fluorine substituent, givin...
Figure 8: Some iminosugars are “privileged structures” that serve as valuable drug leads.
Figure 9: Fluorinated iminosugar analogues 32–34 illuminate the binding interactions of the α-glycosidase inh...
Figure 10: Fluorinated miglitol analogues, and their inhibitory activity towards yeast α-glycosidase.
Figure 11: Analogues of isofagomine (31) have different pKaH values, and therefore exhibit maximal β-glucosida...
Scheme 3: General strategy for the synthesis of fluorinated N-heterocycles via deoxyfluorination.
Figure 12: Late stage deoxyfluorination in the synthesis of multifunctional N-heterocycles.
Scheme 4: During the deoxyfluorination of N-heterocycles, neighbouring group participation can sometimes lead...
Scheme 5: A building block approach for the synthesis of fluorinated aziridines 2 and 3.
Scheme 6: Building block approach for the synthesis of a difluorinated analogue of calystegine B (63).
Scheme 7: Synthesis of fluorinated analogues of brevianamide E (65) and gypsetin (68) via electrophilic fluor...
Scheme 8: Organocatalysed enantioselective fluorocyclisation.
Scheme 9: Synthesis of 3-fluoroazetidine 73 via radical fluorination.
Scheme 10: Synthesis of 3,3-difluoropyrrolidine 78 via a radical cyclisation.
Scheme 11: Chemoenzymatic synthesis of fluorinated β-lactam 4b.