CF3CO2ZnEt-mediated highly regioselective rearrangement of bromohydrins to aldehydes
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Abstract Tropone dimethyl acetal (I) reacts with the organolithium compounds (II) to form selectively the 4‐substituted products (III) which are rearranged upon thermolysis, yielding the isomers (IV).
Tropone
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Abstract Reductive ring-opening reactions of the 4,6-O-benzylidene derivatives of methyl 3-deoxy-β-d-arabino-, 3-deoxy-α-d-ribo-, and 2-O-benzyl-3-deoxy-α-d-ribo-hexopyranosides with LiAlH4 and AlCl3 in the molar ratio of 4 : 4 gave the 4- and 6-O-benzyl derivatives in a ratio of 7 : 3. The product ratios for the reactions of methyl 4,6-O-benzylidene-2,3-dideoxy-2-fluoro-α-d-arabino- and β-d-ribo-hexopyranosides and methyl 2-O-benzyl-4,6-O-benzylidene-3-deoxy-3-fluoro-α-d-gluco- and β-d-allopyranosides were 3 : 2, 2 : 3, 1 : 1, and 3 : 7, respectively. When the molar ratio of the reagents was 2 : 4, however, the product ratios for the reactions of all the above-mentioned 4,6-O-benzylidene derivatives were approximately equal to 4 : 1. The influence of fluorine at C-2 or C-3, as well as that of the molar ratios of LiAlH4 and AlCl3, on the regioselectivity of the reductive cleavage of 4,6-O-benzylidenehexopyranosides are discussed.
Fluorine
Cleavage (geology)
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Abstract The method can be generally applied to the monotosylation of pyranoside derivatives bearing three secondary hydroxyl groups.
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Abstract Reaction of the aliphatic ketones (II) with the chloride (I) gives the monochlorinated ketones (IV) via the intermediates (III).
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Abstract Fluoride ion-catalyzed isomerization of methyl-substituted allylsilanes is reported. In the reaction, a regioisomer of allylsilanes, in which the silicon atom binds to the less substituted carbon atom of the allylic group, is obtained. Accordingly, the reaction is useful as a new route to regioselective synthesis of allylsilanes.
Organosilicon
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Acylation of representative carbohydrate derivatives was accomplished with in situ generated 1-acyloxy-1H-benzotriazoles. The observed high regioselectivity, mild reaction conditions and convenient work-up make the presented one-pot procedure generally applicable and more advantageous than acylations with previously introduced reagents, including N-acylimidazoles.
Reaction conditions
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In the presence of the [Cp*IrCl2]2/NaOH system, the direct N-alkylation of 2-aminoquinazolines and 2-aminopyrimidines with alcohols afforded the N-exosubstituted 2-(N-alkylamino)quinazolines and 2-(N-alkylamino)pyrimidines with 71–96% yields and complete regioselectivities. The protocol is highly attractive because of easily available starting materials, high atom efficiency and environmental friendliness.
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The investigated compounds in DMSO solution unexpectedly alkylate the N9 nitrogen of 2′-deoxyadenosine, whereas the N6 nitrogen atom is alkylated in water solution.
Deoxyadenosine
Nitrogen atom
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