Asymmetric Syntheses of Enantiopure 4-Substituted Pipecolic Acid Derivatives

Agami, Claude; Bisaro, Fabrice; Comesse, Sébastien; Guesné, Sébastien; Kadouri‐Puchot, Catherine; Morgentin, Rémy

doi:10.1002/1099-0690(200106)2001:12<2385::aid-ejoc2385>3.0.co;2-z

Cited by 21 publications

(7 citation statements)

References 28 publications

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“…Despite several racemic syntheses of 4-methylpipecolic acid, only a limited number of asymmetric syntheses have been described. Asymmetric synthesis of 4-methylpipecolic acid has been accomplished by aza-Diels−Alder reaction, intramolecular ene-iminium cyclization, and Sharpless epoxidation followed by ring-closing metathesis . Disappointingly, most of these methods proceed with low overall stereoselectivity.…”

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Synthesis of Methyl N-Boc-(2S,4R)-4-methylpipecolate

2010

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An efficient stereoselective synthesis of fully protected (2S,4R)-4-methylpipecolic acid has been developed. The synthesis was achieved by initial asymmetric α-alkylation of glycine with a chiral iodide, affording the linear precursor as a single stereoisomer. Subsequent aldehyde formation using OsO(4)/NaIO(4) followed by immediate intramolecular cyclization afforded an enamine that was then subjected to hydrogenation to give the final compound in 23% yield over 10 steps.

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Synthesis of Methyl N-Boc-(2S,4R)-4-methylpipecolate

2010

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“…A different approach to azabicycles is the use of bis(electrophilic) aldehydes in aza‐Prins cyclizations. Puchot devised an elegant route for the synthesis of pipecolic acids, in which the key step was the stereoselective reaction between a chiral allylsilyl β‐amino alcohol and glyoxal. The dual condensation of the bis(nucleophilic) amino alcohol with glyoxal gives an intermediate hemiacetal iminium ion, which is readily captured by the allylsilane to afford a bicyclic compound with an exocyclic double bond (Scheme ).…”

Section: Synthesis Of Azacycles By Silyl‐prins Cyclizationmentioning

confidence: 99%

Synthesis of O‐ and N‐Heterocycles by Silyl‐Prins Cyclization of Allylsilanes

Díez-Poza

Barbero

2017

Eur J Org Chem

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Prins cyclization has emerged as one of the most valuable methods for the construction of heterocycles. It proceeds through intramolecular addition of a π‐nucleophile to an oxocarbenium or related ion. The use of electron‐rich alkenes, such as allylsilanes (so‐called silyl‐Prins cyclization) offers the benefit of allowing more selective reactions. The regio‐ and stereochemical outcomes of these transformations are explained by well‐stablished transition states. This review presents the most important contributions involving silyl‐Prins cyclization to the stereoselective preparation of oxygen and nitrogen heterocycles. The influence of different structural variants in the selectivity of the cyclization is discussed. These reactions have frequently been used as key steps in the synthesis of a wide variety of natural products.

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“…[10][11][12] In a preliminary report, 13 we disclosed the facile preparation of building blocks 1a and 1b (Fig. 1), obtained by the condensation of (R)-(À)-phenylglycinol with a mesotrihydroxylated glutaraldehyde.…”

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confidence: 98%