Stereoselective Synthesis of 2,6-Disubstituted 3-Piperidinols:  Application to the Expedient Synthesis of (+)-Julifloridine

Lemire, Alexandre; Charette, André B.

doi:10.1021/ol051022z

Cited by 68 publications

(23 citation statements)

References 31 publications

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“…Charette and co‐workers showed a different approach for the synthesis of (+)‐julifloridine ( 75 ), in which the chirality was induced through the formation of a chiral salt by the condensation of pyridine with an enantiopure amide (Scheme ) 54. After this condensation a Grignard reagent was added in the same pot to form product 73 in a regio‐ and diastereoselective fashion.…”

Section: Reduction Of Pyridine Derivatives To Piperidine Ringsmentioning

confidence: 99%

The 3‐Hydroxypiperidine Skeleton: Key Element in Natural Product Synthesis

2010

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Section: Reduction Of Pyridine Derivatives To Piperidine Ringsmentioning

confidence: 99%

The 3‐Hydroxypiperidine Skeleton: Key Element in Natural Product Synthesis

2010

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“…Charette has also reported the use of pyridinium salt alkylation for the preparation of AL [27]. In this synthetic route diastereoselective addition of Grignard reagent to a chiral pyridinium salt (generated by pyridine and amide 108) secured the 2-dihydropyridine derivative 109 (Scheme 18).…”

Section: Pyridinium Salt Alkylationmentioning

confidence: 99%

Stereoselective Syntheses of 2,6-disubstituted Piperidin-3-oles (alkaloid lipids)

Koulocheri¹,

Pitsinos²,

Haroutounian

2008

COC

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Alkaloid lipids comprise a class of natural compounds with significant biological activities of medicinal interest. Their structural framework consists of a 2,6-disubstituted-3-piperidinol moiety (polar head group) and a lipid tail. Representative examples of alkaloid lipids are (+)-Cassine, ( )-Prosophylline, ( )-Prosopinine, ( )-Spectalline.Many synthetic strategies have been developed for the efficient stereoselective synthesis of various natural alkaloid lipids and their synthetic analogues. This mini-review focuses on the most successful approaches published during the new millennium. The synthetic strategies are grouped in two main sections, depending on whether the lipophilic side chain is introduced before ("early") or after ("late") piperidine ring formation. These sections are further organised based on the key ring forming reaction/strategy employed.For the strategies that opt to introduce the lipophilic side chain early on the synthetic sequence, the intramolecular reductive amination, either with or without isolation of the intermediate imine/enamine, constitutes one of the most popular methods for constructing the piperidine ring followed closely by approaches based on the intramolecular alkylation of suitable amine derivatives. Olefin ring closing metathesis and intramolecular hetero-Diels-Alder reactions have also been exploited to secure the azaheterocycle.The intramolecular alkylation of an amine or the, retrosynthetically related, intramolecular amine addition to an olefin have also been employed as key ring-forming reactions by syntheses that adopt the more convergent approach of introducing the side chain on a preformed heterocycle. In this regard the introduction of the side chain via alkylation of pyridinium salts, alkylation of a lactam (2-piperidone) or glutarimide derivatives have been investigated. Several groups have also exploited the oxidative cyclization of -furylamines to prepare 2-dihydropyridones as a convenient scaffold for the late introduction of the lipid tail.In some cases, carbohydrates and aminoacids were used (either as starting materials or as chiral auxiliaries) for the enantioselective synthesis of alkaloid lipids. Enzymatic or chemical (Jacobsen's epoxide hydrolysis protocol) resolutions of racemic starting materials and Sharpless asymmetric epoxidation, dihydroxylation or aminohydroxylation of olefins have also been utilized.Finally, it is noteworthy that in several cases, apart from the Witting reaction and the use of Grignard reagents, olefin cross-metathesis has also been successfully employed for the introduction of the lipid side chain.

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“…Cyclic enamines bearing an electron‐withdrawing protecting group on nitrogen, such as ene‐sulfonamide 1 a , have been shown to be useful precursors to oxygenated piperidines by hydroboration–oxidation, epoxidation‐ring opening and by dihydroxylation . This chemistry has been used in this laboratory for the stereoselective synthesis of pseudoconhydrine, azimic acid, and 5‐hydroxysedamine .…”

Section: Introductionmentioning

confidence: 99%

Platinum‐Catalysed Ring‐Opening Isomerisation of Piperidine Cyclopropanes

2018

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Ar ange of cyclopropyl-fused N-tosyl piperidines have been synthesised ands hown to undergo ring-opening isomerisation on treatment with platinum(II) catalysts. The products can have either an endo-cyclic or exo-cyclic double bond. The selectivity is influenced by reaction temperature, solventa nd, most significantly,t he catalyst. Am echanism in-volvingC ÀCb ond activation and b-hydride eliminationi s proposed. When b-hydride elimination is blocked, as tereospecific platinum-driven Wagner-Meerwein shift is observed.

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Stereoselective Synthesis of 2,6-Disubstituted 3-Piperidinols: Application to the Expedient Synthesis of (+)-Julifloridine

Cited by 68 publications

References 31 publications

The 3‐Hydroxypiperidine Skeleton: Key Element in Natural Product Synthesis

The 3‐Hydroxypiperidine Skeleton: Key Element in Natural Product Synthesis

Stereoselective Syntheses of 2,6-disubstituted Piperidin-3-oles (alkaloid lipids)

Platinum‐Catalysed Ring‐Opening Isomerisation of Piperidine Cyclopropanes

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