Macrocycle Synthesis by Olefin Metathesis on a Nanosized, Shape‐Persistent Tricationic Platinum Template

Chuchuryukin, Aleksey V.; Dijkstra, Harm P.; Suijkerbuijk, Bart M. J. M.; Gebbink, Robertus J. M. Klein; Klink, Gerard P. M. van; Mills, Allison M.; Spek, Anthony L.; Koten, Gerard van

doi:10.1002/ange.200390054

Cited by 29 publications

(22 citation statements)

References 16 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…However, a steep drop in yield from 44% with the first generation catalyst to 20% of the macroheterocycle 21e was observed, Table 1, entries 5 and 6 [64]. In addition, larger quantities of higher generation oligomers were observed, pointing to competitive ring-opening metathesis or cross-metathesis reactions degrading the yield of trimer.…”

Section: Templated Synthesis Of Pyridine-containing Macroheterocyclesmentioning

confidence: 99%

“…AgBF 4 quantitatively forms the templated precursor 19, see Scheme 5. Subjecting this complex to RCM with 5 mol% of first generation Grubbs catalyst 1 in dilute conditions (1 mmol/L), followed by decomplexation of the pyridines from the tripincer template with NaCl, afforded the macroheterocycle 21a in 67% yield as a mixture of cis/trans isomers [64]. Remarkably, this equates to a yield per olefin coupling of 88%; the selectivity for generation of this single product is quite high.…”

Section: Templated Synthesis Of Pyridine-containing Macroheterocyclesmentioning

confidence: 99%

“…All other reagents were purchased from Acros or Aldrich and used as received. The preparation of all complexes not specifically listed here can be found in the literature [63][64][65][66].…”

Section: General Considerationsmentioning

confidence: 99%

See 2 more Smart Citations

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Chase

Lutz

Spek

et al. 2006

Journal of Molecular Catalysis A: Chemical

Self Cite

View full text Add to dashboard Cite

Templation is a well-known strategy for the selective generation of complex products. Ring-closing metathesis, catalyzed by well-characterized Ru and Mo catalysts, is a powerful method for C C bond formation and has certainly developed into one of the most important modern reactions in organic synthesis and in polymer chemistry. Despite the extensive research on this reaction, the use of organometallic containing substrates is not well-studied. Here, we give a detailed account of our ongoing efforts to employ ring-closing metathesis with bis(␣-olefin) substituted pyridines in the presence of trimeric metallopincer templates for the selective synthesis of macroheterocycles with ring sizes up to 81 atoms.

show abstract

Section: Templated Synthesis Of Pyridine-containing Macroheterocyclesmentioning

confidence: 99%

Section: Templated Synthesis Of Pyridine-containing Macroheterocyclesmentioning

confidence: 99%

See 1 more Smart Citation

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Chase

Lutz

Spek

et al. 2006

Journal of Molecular Catalysis A: Chemical

Self Cite

View full text Add to dashboard Cite

show abstract

“…[15] Here we report a full account of the use of this shape-persistent tri-metallic template for the general synthesis of macroheterocycles of several compositions.…”

Section: Introductionmentioning

confidence: 99%

General Approach for Template‐Directed Synthesis of Macroheterocycles by Ring‐Closing Metathesis (RCM)

et al. 2005

View full text Add to dashboard Cite

Dedicated to Prof. Dr. Richard Schrock on the occasion of his 60 th birthday and in recognition of his highly appreciated contribution to chemistry in general and his pioneering studies on ofefin metathesis in particular.Abstract: A general method to prepare macroheterocycles is reported in which a rigid symmetric platinated tris-pincer tricationic complex (3) is used as a template. The system uses bisolefin functionalized pyridine ligands (1, 2) which selectively bind to the three platinum centers of the template resulting in pre-organization of the olefinic tails. By subjecting these pre-organized complexes (4) to olefin metathesis reaction conditions, the olefinic tails were interconnected affording several macroheterocycles of different compositions and sizes. Various pyridines with different substitution patterns (2,6-and 3,5-disubstituted) and different olefinic tails (aliphatic, polyether, and styryl) were synthesized and used in the cyclization reactions, showing the diversity of this method. It was found that only the use of 2,6-disubstituted pyridines resulted in the formation of the desired macrocycles while 3,5-difunctionalized pyridines gave only pyridinophane formation. Furthermore, the length of the olefinic tails needs to be at least eleven atoms (C or O) in order to suppress oligomerization in favor of macrocycle formation. Yields of up to 70% of the macrocycles were obtained using the first-generation [Cl 2 (Cy 3 P) 2 Ru ¼ CHPh] or second-generation [Cl 2 (Cy 3 P)(IMes)Ru ¼ CHPh] Grubbs catalysts. Reactions of the platinated pincer pyridines with Schrock Mo-based metathesis catalysts results in exclusive olefin isomerization and no productive metathesis. The generated macrocycles (hosts) could effectively be separated from the template by addition of aqueous sodium chloride and reattached to the (recycled) template (guest). The X-ray structure determination of host-guest complex 10 is the definite proof for this reattachment and the perfect cyclic structure of the macrocycle.

show abstract

“…SCS-pincer Pd, and NCN-pincer Pd and Pt groups with functional para-substituents suited for covalent or non-covalent binding, have been applied by several researchers as building blocks for supramolecular systems such as coordination dendrimers [20Ϫ22], coordination polymers [23,24], and giant macrocycles [25,26]. Here, we report on the synthesis and characterization of a new supramolecular building block, in which two NCN-pincer Pt II units are linked to a tin(IV) porphyrin through a Sn-O bond to the tin center of a tin(IV) porphyrin dication.…”

Section: Introductionmentioning

confidence: 99%

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

Suijkerbuijk

Tooke

Spek

et al. 2007

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

Abstract.A tin(IV) porphyrin was combined with two axial NCNpincer platinum(II) fragments by utilizing the oxophilicity of the apical positions on the tin atom and the acidic nature of the NCNpincer platinum derived benzoic acid. The solid-state structure determined by X-ray crystallography revealed some close contacts between the pincer complexes and the meso-p-tolyl subsitutents of the porphyrin. It was shown by 1 H NMR spectroscopy that these

show abstract

Macrocycle Synthesis by Olefin Metathesis on a Nanosized, Shape‐Persistent Tricationic Platinum Template

Abstract: Ein 69‐gliedriger Ring (siehe Bild) entsteht bei einer Metathesereaktion, die ein metalliertes Tris(pinzetten)‐substituiertes Benzol als Gerüst verwendet. Das makrocyclische Produkt kann durch Zugabe von Cl− vom Templat abgespalten und das Templat quantitativ zurückgewonnen werden.

Cited by 29 publications

References 16 publications

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

Ring closing metathesis employing organometallic substrates and the templated synthesis of macrocycles

General Approach for Template‐Directed Synthesis of Macroheterocycles by Ring‐Closing Metathesis (RCM)

A Tin(IV) Porphyrin with Two Axial Organometallic NCN‐Pincer Platinum Units

Contact Info

Product

Resources

About