Recent Advances on the Synthesis of Piperidines through Ruthenium-Catalyzed Ring-Closing Metathesis (RCM) Reactions

Merino, Pedro; Tejero, Tomás; Greco, Graziella; Marca, Eduardo; Delso, Ignacio; Gómez-SanJuan, Asier; Matute, Rosa

doi:10.3987/rev-11-sr(p)1

Cited by 33 publications

(8 citation statements)

References 125 publications

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“…Due to that, a large number of classical methodologies have been used for their synthesis, in which the key step is the generation of the six-membered ring, including the aldol reaction, the reductive amination, Mannich reaction, ring closing metathesis, Diels-Alder reaction with imines as dienophiles, aza-Prins cyclization, and intramolecular Michael reaction, among others [110][111][112][113][114][115]. Despite the considerable effort made to date in this field, the development of new methodologies that allow accessing these heterocycles in a stereoselective way, and taking into account environmental considerations as one of the most important points, continue to be of great interest [109,[116][117][118].…”

Section: Asymmetric Synthesis Of Piperidinesmentioning

confidence: 99%

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Mendes¹,

Costa²,

Yus³

et al. 2021

Beilstein J. Org. Chem.

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The synthesis of nitrogen-containing heterocycles, including natural alkaloids and other compounds presenting different types of biological activities have proved to be successful employing chiral sulfinyl imines derived from tert-butanesulfinamide. These imines are versatile chiral auxiliaries and have been extensively used as eletrophiles in a wide range of reactions. The electron-withdrawing sulfinyl group facilitates the nucleophilic addition of organometallic compounds to the iminic carbon with high diastereoisomeric excess and the free amines obtained after an easy removal of the tert-butanesulfinyl group can be transformed into enantioenriched nitrogen-containing heterocycles. The goal of this review is to the highlight enantioselective syntheses of heterocycles involving the use of chiral N-tert-butanesulfinyl imines as reaction intermediates, including the synthesis of several natural products. The synthesis of nitrogen-containing heterocycles in which the nitrogen atom is not provided by the chiral imine will not be considered in this review. The sections are organized according to the size of the heterocycles. The present work will comprehensively cover the most pertinent contributions to this research area from 2012 to 2020. We regret in advance that some contributions are excluded in order to maintain a concise format.

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Section: Asymmetric Synthesis Of Piperidinesmentioning

confidence: 99%

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Mendes¹,

Costa²,

Yus³

et al. 2021

Beilstein J. Org. Chem.

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“…Given their immense pharmaceutical utilities, the synthesis of piperidines has been extensively studied 1c,e–i. Hydrogenation of easily accessible pyridines provides probably the most economic and efficient route for accessing piperidines 7.…”

Section: Effect Of Metal Compounds and Iodide On The Transfer Hydrogementioning

confidence: 99%

Efficient and Chemoselective Reduction of Pyridines to Tetrahydropyridines and Piperidines via Rhodium‐Catalyzed Transfer Hydrogenation

Wu¹,

Tang²,

Pettman³

et al. 2012

Adv Synth Catal

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Promoted by iodide anion the rhodium complex dimer, [Cp*RhCl 2 ] 2 , catalyzes efficiently the transfer hydrogenation of various quaternary pyridinium salts under mild conditions, affording not only piperidines but also 1,2,3,6-tetrahydropyridines in a highly chemoselective fashion, depending on the substitution pattern at the pyridinium ring. The reduction is conducted in azeotropic formic acid/triA C H T U N G T R E N N U N G ethylamine (HCOOH-Et 3 N) mixture at 40 8C, with catalyst loadings as low as 0.005 mol% being feasible.

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“…Initial attempt following several known reaction conditions with Grubbs II 18,20,24,28,29 failed to provide the desired unsaturated 1-azabicyclo[ 5.4 .0]tridecane core of 7 . A perusal of the literature regarding RCM methods with tertiary amines, suggested that ‘protection’ of the amine by in situ generation of ammonium salts enabled facile ring-closing.…”

mentioning

confidence: 99%

“…A perusal of the literature regarding RCM methods with tertiary amines, suggested that ‘protection’ of the amine by in situ generation of ammonium salts enabled facile ring-closing. 29–31 Thus, treatment of 21c1 with 1.1 equivalent of camphor sulfonic acid (CSA) in 0.05 M toluene, followed by the addition of 10 mol% of Grubbs II and microwave heating for 1 hour at 100 °C, provided the unsaturated 1-azabicyclo[ 5.4 .0]tridecane core of 7 in 70% isolated yield (Scheme 5). 27 An evaluation of additional acids led to the use of trifluoroacetic acid (TFA), which was equally effective (68% yield) and allowed for simpler purification.…”

mentioning

confidence: 99%

A general, enantioselective synthesis of 1-azabicyclo[m.n.0]alkane ring systems

Senter

Schulte

Konkol

et al. 2013

Tetrahedron Letters

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In this Letter, we describe a novel approach for the general and enantioselective synthesis of a diverse array of small to large 1-azabicyclo[m.n.0]alkyl ring systems with an embedded olefin handle for further functionalization. The stereochemistry is established via a highly diastereoselective indium-mediated allylation of an Ellman sulfinimine in greater than 9:1 dr., which is readily separable by column chromatography to afford a single diastereomer. This methodology allows for the rapid preparation of 1-azabicyclo[m.n.0]alkane ring systems that are not readily accessible through any other chemistry in excellent overall yields and, for many systems, the only enantioselective preparation reported to date.

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Recent Advances on the Synthesis of Piperidines through Ruthenium-Catalyzed Ring-Closing Metathesis (RCM) Reactions

Cited by 33 publications

References 125 publications

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

N-tert-Butanesulfinyl imines in the asymmetric synthesis of nitrogen-containing heterocycles

Efficient and Chemoselective Reduction of Pyridines to Tetrahydropyridines and Piperidines via Rhodium‐Catalyzed Transfer Hydrogenation

A general, enantioselective synthesis of 1-azabicyclo[m.n.0]alkane ring systems

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