A ring-closing metathesis-mediated route to novel enantiopure conformationally restricted cyclic amino acids

Tjen, Kim C. M. F.; Kinderman, Sape S.; Hiemstra, Henk; Rutjes, Floris P. J. T.

doi:10.1039/b001253j

Cited by 36 publications

(13 citation statements)

References 13 publications

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“…The group of Rutjes reported an elegant combination of palladium-catalyzed N,O-acetal formation, ruthenium-catalyzed ring-closing metathesis, and N-sulfonyliminium ion-mediated carbon-carbon bond formation approach [20] to synthesize a series of enantiomerically pure 2,6-disubstituted unsaturated pipecolic acid derivates like 15, as shown in Scheme 4.…”

Section: Synthesis Of Conformationally Restricted Amino Acids and Pepmentioning

confidence: 99%

“…Functionalization of this scaffold by different R groups (to give molecular entity 15) was performed with a variety of nucleophiles in the presence of BF 3 ÁEt 2 O as Lewis acid. In case of Et 3 SiH (R¼H) as the nucleophile, unsaturated pipecolic acid derivative 17 (baikiain [21]) was obtained in 88% yield [20]. Pipecolic acid derivatives are present in several natural products with important medicinal properties like the immunosuppressants FK506 [22] and rapamycin [23].…”

Section: Synthesis Of Conformationally Restricted Amino Acids and Pepmentioning

confidence: 99%

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Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Rijkers

2015

Topics in Heterocyclic Chemistry

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This review surveys developments in the field of ring-closing metathesis and cross-metathesis reactions applied to the synthesis of constrained amino acids, peptides, and peptidomimetics. Examples, in which metathesis is used as one of the synthetic tools to arrive at the desired peptide molecules as well as examples that describe in-depth optimized metathesis protocols, will be discussed. Currently, metathesis reactions are well-accepted synthetic tools within the field of peptide chemistry and provide peptides unprecedented properties like conformational, metabolic, and chemical stability and improved bioactivity.

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Section: Synthesis Of Conformationally Restricted Amino Acids and Pepmentioning

confidence: 99%

Section: Synthesis Of Conformationally Restricted Amino Acids and Pepmentioning

confidence: 99%

Synthesis of Cyclic Peptides and Peptidomimetics by Metathesis Reactions

Rijkers

2015

Topics in Heterocyclic Chemistry

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“…Baikiain (175), another example of a natural product containing the pipecolic acid core structure, was synthesized in 2000 by Rutjes et al via a metathesis route [63]. Amidopalladation of methyl propadienyl ether with the enantiopure l-allylglycine derivative 172 provided the RCM precursor 173 in good yield.…”

Section: Six-membered Nitrogenmentioning

confidence: 99%

Natural Products Containing Medium‐Sized Nitrogen Heterocycles Synthesized by Ring‐Closing Alkene Metathesis

Broek

Meeuwissen

Delft

et al. 2010

Metathesis in Natural Product Synthesis

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The formation of carbon-carbon bonds is a crucial issue in organic synthesis. Out of all methodologies available, the metathesis reaction has, over the past decade, evolved as one of the most useful tools in this field to rapidly construct the skeleton of carba-and heterocyclic molecules [1]. Key step of the metathesis reaction entails the metal-catalyzed redistribution of two carbon-carbon double bonds by a scission-recombination process [2]. Among various applications of the metathesis reaction, ring-closing metathesis (RCM) has emerged as one of the most powerful tools for the construction of natural and unnatural cyclic compounds (Scheme 2.1) [3]. Other types of metathesis reactions developed so far include cross-metathesis (CM), ring-opening metathesis (ROM), ring rearrangement metathesis (RRM, combining ROM with RCM in a tandem sequence), and ene-yne metathesis [3].The metathesis reaction has already been used for several decades in polymer chemistry for ring-opening metathesis polymerization (ROMP) [4]. Only since the development of well-defined molybdenum and ruthenium carbene complexes by Schrock [5] and Grubbs [6] in 1990 and 1992, respectively, an explosion of their application in organic synthesis has been witnessed. Initially, it was demonstrated that the Schrock catalyst [Mo]-I could serve as a homogeneous catalyst for olefin RCM [7]. Unfortunately, metal carbene complex [Mo]-

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“…Despite these drawbacks, two reasons stimulated us to start investigating the reactivity of N-phosphoryliminium ions 3: (i) the lack of knowledge of nucleophilic additions onto such ions, and (ii) the ready availability of the required precursors through a novel amidopalladation that was recently developed in our group. 7 Furthermore, we anticipated that by selecting a chiral phosphoryl moiety, it might be possible to perform the addition reactions in a diastereoselective fashion. In this contribution, our recent findings involving the synthesis and reactivity of N-phosphoryliminium ions in C-C bond formation is described in detail.…”

Section: Scheme 1 Literature Examplesmentioning

confidence: 99%

“…The cyclic allylglycine-derived precursor 11 was synthesized following the pathway that was previously developed in our group for the corresponding carbamates (Scheme 2). 7 Pd-catalyzed amidation of 8 with benzyl propadienyl ether (benzyloxyallene) proceeded reasonably well at 60 °C and provided the allylic N,O-acetal 9 in 55% isolated yield. 8 This diolefin was then ring-closed using the second generation Grubbs catalyst (10), which gave a significantly higher yield than other existing Ru catalysts.…”

Section: Scheme 1 Literature Examplesmentioning

confidence: 99%