Synthesis of 3-aminopyrrolidines by cyclization of neutral C-centered α-aminoalkyl radicals

Suero, Rubén; Gorgojo, Jose M.; Aurrecoechea, José M.

doi:10.1016/s0040-4020(02)00621-x

Cited by 10 publications

(8 citation statements)

References 71 publications

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“…The SmI 2 -mediated one-electron reduction of condensation adducts derived from aldehydes, secondary amines, and benzotriazole 4 has become a practical method for generation of α-aminoalkyl radicals capable of radical cyclization, as shown by the corresponding reports on the preparation of cyclopentylamines,22a pyrrolidines, 22b-e and piperidines 22f. At the outset, the possibility of applying this methodology using amines 4 , 9 , or 10 raised some concerns.…”

Section: Resultsmentioning

confidence: 99%

Divergent Synthetic Strategy Leading to Structurally Diverse Pyrrolidines and Piperidines from Common γ-Aminoalkyl Butenolide and Aldehyde Precursors

Aurrecoechea

Suero

2006

J. Org. Chem.

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Condensation between aldehydes and the secondary amino function of 5-(aminoalkyl)furan-2(5H)-ones, obtained by the silyloxyfuran dienolate addition to imine-type derivatives, produces either aminoalkylbenzotriazoles or 1,2,3,4-tetrahydropyridines. The former can be reduced with SmI2 to generate alpha-aminoalkyl radicals that are trapped by the alpha,beta-unsaturated lactone moiety yielding substituted pyrrolidines diastereoselectively, while catalytic hydrogenation of the latter affords isomeric piperidine analogues. Alternatively, SmI2-promoted reduction of tetrahydropyridines in the presence of acid also leads to intermediate alpha-aminoalkyl radicals that participate in inter- or intramolecular olefin addition reactions. Further manipulation of the lactone functionality in various ways gives access to a number of interesting derivatives based upon either a pyrrolidine or a piperidine structural motif. As a result, a high degree of structural diversity is obtained in a few steps starting from a common set of simple materials.

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Section: Resultsmentioning

confidence: 99%

Divergent Synthetic Strategy Leading to Structurally Diverse Pyrrolidines and Piperidines from Common γ-Aminoalkyl Butenolide and Aldehyde Precursors

Aurrecoechea

Suero

2006

J. Org. Chem.

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“…The resulting solution was stirred at room temperature for 40 h. The solvent was evaporated and the residue was purified by chromatography to give the pure product (2.86 g, 50 % yield) as a light yellow oil. 1 Substrate S8: A mixture of methyl (E)-5-aza-5-benzyl-7-oxohept-2-enoate [28] (15 mmol, 3.71 g) and (benzoylmethylene)triphenylphosphorane (7.6 g, 20 mmol) in CH 2 Cl 2 (20 mL) was allowed to stir at room temperature for 16 h. The solvent was removed to give the crude product which was purified by flash chromatography. The pure product was isolated in 65 % yield (4.54 g).…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Enantioselective Intramolecular Conjugate Addition/Trapping Reactions: Synthesis of Cyclic Compounds with Multichiral Centers

Alexakis

2007

Chemistry A European J

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The Cu-catalyzed enantioselective conjugate addition of dialkylzinc to bis-alpha,beta-unsaturated carbonyl compounds followed by the intramolecular trapping of the zinc enolate in the presence of chiral phosphoramidite ligands was investigated. Cyclic and heterocyclic compounds with multichiral centers were formed as a mixture of two diastereomers with excellent diastereoselectivities (up to 99:1) and enantioselectivities (up to 94 % ee, ee=enantiomeric excess). The stereochemistry was determined to be trans,trans for the major products and trans,cis for the minor products. The absolute configuration of the cyclic compounds was assigned by comparison with the analogous adduct derived from trans-3-nonen-2-one and Et(2)Zn or the adduct obtained through conjugate addition of Me(2)Zn to trans-1-phenyl-non-2-en-1-one. Further transformation of these cyclic products into more complex compounds is under investigation in our laboratory.

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“…33) has been achieved in good yield (Scheme 10). 58 The radical precursor 32 Scheme 9 Reagents and conditions: i, PhSH (0.2 equiv. ), AIBN, benzene, reflux, 95% (29 : 30 = 1 : 1.5) was synthesised from the respective aldehyde 31 by addition of an amine and α-benzotriazole (Bt-H) and treated with SmI 2 in a one-pot reaction.…”

Section: Nitrogen Heterocyclesmentioning

confidence: 99%

Synthesis of heterocycles by radical cyclisation

Bowman

Fletcher

Potts

2002

J. Chem. Soc., Perkin Trans. 1

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Synthesis of 3-aminopyrrolidines by cyclization of neutral C-centered α-aminoalkyl radicals

Cited by 10 publications

References 71 publications

Divergent Synthetic Strategy Leading to Structurally Diverse Pyrrolidines and Piperidines from Common γ-Aminoalkyl Butenolide and Aldehyde Precursors

Divergent Synthetic Strategy Leading to Structurally Diverse Pyrrolidines and Piperidines from Common γ-Aminoalkyl Butenolide and Aldehyde Precursors

Copper‐Catalyzed Enantioselective Intramolecular Conjugate Addition/Trapping Reactions: Synthesis of Cyclic Compounds with Multichiral Centers

Synthesis of heterocycles by radical cyclisation

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