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Useful Intermediates (useful + intermediate)

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Chemistry100%

Selected Abstracts

Synthesis of 14C-labeled piperidines and application to synthesis of [14C]SCH 351125, a CCR5 receptor antagonist

JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 7 2007
Sumei Ren
Abstract 1-Benzyl-4-hydroxy[2- 14C]piperidine, a useful intermediate in labeled compound synthesis, was prepared from [14C]formaldehyde in high yield. The distribution pattern of 14C in the product is consistent with a mechanism involving reversible iminium ion formation and rapid equilibration of the iminium ion through a cationic aza-Cope rearrangement. These steps precede the rate-determining intramolecular cyclization step. SCH 351125 is a potent, selective CCR5 receptor antagonist with potential as a treatment for HIV infection. [14C]SCH 351125, required for metabolism studies, was prepared from 1-benzyl-4-hydroxy[2- 14C]piperidine in six steps. [14C]SCH 351125 is a mixture of four atropisomers. Preparation of [14C]SCH 351125 besylate salt of the desired atropisomer pair is also described. Copyright © 2007 John Wiley & Sons, Ltd. [source]

Rhodium-Catalyzed Asymmetric Nitroallylation of Arylmetallics with Cyclic Nitroallyl Acetates and Applications in Organic Synthesis

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2006
Lin Dong
Abstract Highly enantioselective rhodium-catalyzed nitroallylations of arylboronic acids and arylzinc chlorides with cyclic nitroallyl acetates are described. Catalyst screening indicated that the rhodium complex of [Rh(OH)(COD)]2 and optically pure binap is the optimal catalyst for the nitroallylation of arylboronic acids with 2-nitrocyclohex-2-enyl esters, providing good yields and high enantioselectivities of up to 99,% ee. The rhodium complex prepared from Rh(acac)(C2H4)2 and (R)-binap efficiently catalyzed the nitroallylation of arylzinc chlorides with 2-nitrocyclohex-2-enyl acetate at 0 °C in high yields of up to 93,% and with high enantioselectivities of up to 96,% ee. A number of synthetically useful intermediates with high optical purity were prepared with this reaction as starting point: concise total syntheses of optically pure (+)-,-lycorane in 53,% overall yield and of (+)-,-lycorane in 52,% overall yield were achieved by commencing with the asymmetric nitroallylation of 3,4-methylenedioxyphenylzinc chloride with 2-nitrocyclohex-2-enyl acetate. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source]

A Novel Oxime-Derived Solid Support for the Synthesis of 3-Phosphorylated Oligonucleotides

HELVETICA CHIMICA ACTA, Issue 10 2003
Simon
Oligonucleotides containing terminal phosphate groups serve as useful intermediates for different applications in molecular and cell biology, as well as for diagnostic purposes. The chemical synthesis of these derivatives has been an important topic of oligonucleotide research. We report here a novel polystyrene-based solid support bearing an , -hydroxy oximate linker that allows the synthesis of 3,-phosphorylated oligodeoxynucleotides as well as oligoribonucleotides in high quality. The formation of the phosphorylated oligonucleotides likely proceeds through an eliminative pathway with concurrent nitroso-ene production. [source]

Organocatalytic Multicomponent ,-Methylenation/Diels,Alder Reactions: A Versatile Route to Substituted Cyclohexenecarbaldehyde Derivatives

CHEMISTRY - A EUROPEAN JOURNAL, Issue 17 2008
Yue Zou
Abstract This article describes the design and optimization of an effective organocatalytic three-component domino ,-methylenation/Diels,Alder reaction to produce vinyl-substituted cyclohexenecarboxaldehydes in a highly regioselective fashion. In these one-pot transformations, 2-formyl-1,3-butadienes (4) were prepared in situ from ,,,-unsaturated aldehydes and formalin and were subsequently trapped with a variety of buta-1,3-dienes. The outcomes of the reactions were dependent on the electronic properties of the dienes. 1-Vinylcyclohexenecarbaldehydes 6 were formed by use of acyclic electron-rich dienes, while the initially formed cycloadducts of 4 with cyclopentadiene underwent Cope rearrangements, leading to the formation of tetrahydro-3H -indene-5-carbaldehyde compounds 7. The mechanisms involved in these reactions were deduced from experimental findings. Furthermore, the method was also extended to one-pot domino methylenation/Diels,Alder reactions of dihydrofurans and dihydropyrans to yield spirocyclic lactols 22. In these reactions, the unstable intermediate hydroxyethyl and hydroxypropyl acroleins behaved as dienophiles, undergoing cycloaddition reactions with dienes with good yields and selectivities. The wide variety of functionalized 1-vinylcyclohex-3-enecarbaldehydes 6, 4-vinylcyclohex-1-enecarbaldehydes 7, and spiro lactols 22 generated through the use of these organocatalytic domino processes as a diversity-oriented synthesis provided useful intermediates for the construction of novel odorants. [source]