A Ring-Closing Metathesis Strategy to Phosphonosugars

Stoianova, Diana S.; Hanson, Paul R.

doi:10.1021/ol016491p

Cited by 41 publications

(28 citation statements)

References 33 publications

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“…Several catalysts have been reported to be tolerant to the presence of heteroatoms and complex or bulky functional groups, and as a result a range of examples of macrocyclic ED‐ROMP precursors are emerging in the literature. Initially, RCM reactions were most commonly employed for the synthesis of complex five‐ to eight‐membered lactams, carbocyclic and heterocyclic vinyl chlorides, alkenylboronates, a variety of phosphorous, sulfur and fluorine containing rings, cyclic di‐ and tri‐nucleotides, and more . Following from these precedents, macrocycle synthesis evolved from simple unsaturated macrolactones and macrolactams, to an even larger range of functional macrocycles such as fluorinated amino and azamacrolactones .…”

Section: Macrocycle Synthesismentioning

confidence: 99%

Recent developments in entropy‐driven ring‐opening metathesis polymerization: Mechanistic considerations, unique functionality, and sequence control

Pearce

Foster

O’Reilly

2019

J. Polym. Sci. Part A: Polym. Chem.

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Entropy‐driven ROMP (ED‐ROMP) involves polymerization of olefin‐containing macrocyclic monomers under entropically favorable conditions. Macrocycles can be prepared from a variety of interesting molecules which, when polymerized, impart unique functionality to the resulting polymer backbone such as degradable linkages, biological moieties, crystallizable groups, or supramolecular hosts. In addition, the sequence of atoms in the cyclic monomer is preserved within the polymer repeating units, allowing for facile preparation of sequence‐defined polymers. In this review article, we consider how the mechanism of ROMP applies to ED polymerizations, how olefinic macrocycles are synthesized, and how polymerization conditions can be tuned to maximize conversion. Recent works in the past 10 years are highlighted, with emphasis on methods which can be employed to achieve fast polymerization kinetics and/or selective head‐to‐tail regiochemistry, thus improving polymerization control. ED‐ROMP, with its unique capability to produce polymers with well‐defined polymer backbone microstructure, represents an essential complement to other, well‐established, metathesis methodologies such as ROMP. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1621–1634

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Section: Macrocycle Synthesismentioning

confidence: 99%

Recent developments in entropy‐driven ring‐opening metathesis polymerization: Mechanistic considerations, unique functionality, and sequence control

Pearce

Foster

O’Reilly

2019

J. Polym. Sci. Part A: Polym. Chem.

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“…Coupling of the phosphonate 63 with an enantiomerically pure diol gave the dienic phosphonate 64 in good yield as mainly one diastereoisomer. RCM of the dienic phosphonate 64 led to the 6-membered ring 65 [32], which was then further elaborated by dihydroxylation and deprotection to give the phosphono-sugar 66 as a single enantiomer. This synthetic sequence again highlights the tolerance of olefin metathesis to a wide variety of functional groups (Scheme 14).…”

Section: Carbohydrate Targetsmentioning

confidence: 99%

Ring Closing Metathesis in the Synthesis of Biologically Interesting Peptidomimetics, Sugars and Alkaloids

Martin¹,

Blechert

2005

CTMC

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Olefin metathesis has rapidly established itself as an essential tool in the synthetic chemist's armoury. The ease of operation and functional group tolerance that is obtained with the modern generation of catalysts makes the use of metathesis an extremely attractive option when preparing medicinally interesting molecules. This article will outline some of the ways in which chemists from both industry and academia have been utilising and developing metathesis in the search for novel biological probes and drug leads.

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“…These so-called phostones have been of some interest in the past, due to their potential application as glycomimetics. [17][18][19] While the 2-ethoxy-2-oxo-1,3-oxaphospholane heterocycle has been known for a long time, 20-21 it has never been used in ROP to the best of our knowledge. The phostone monomers offer several advantages: The P-C bond in the ring reduces monomer synthesis to a single step from inexpensive, less-toxic starting materials, avoiding SOCl2 and POCl3.…”

Section: Introductionmentioning

confidence: 99%

“…Herein, we report the first ring-opening polymerization (ROP) of 2-alkoxy-2-oxo-1,3-oxaphospholanes with both ethyl and butyl side chains, carrying the P–C bond within the ring structure and thus forming in-chain poly(phosphonate)s upon polymerization. These so-called phostones have been of some interest in the past due to their potential application as glycomimetics. − While the 2-ethoxy-2-oxo-1,3-oxaphospholane heterocycle has been known for a long time, , it has never been used in ROP to the best of our knowledge. The phostone monomers offer several advantages: The P–C bond in the ring reduces monomer synthesis to a single step from inexpensive, less-toxic starting materials, avoiding SOCl 2 and POCl 3 .…”

Section: Introductionmentioning

confidence: 99%

Polymerizing Phostones: A Fast Way to In-Chain Poly(phosphonate)s with Adjustable Hydrophilicity

et al. 2018

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Phostones, i.e. 2-alkoxy-2-oxo-1,3-oxaphospholanes, are accessible in a one-pot reaction from commercially available 1,3-dibromopropane and alkyl phosphites. These 5-membered cyclic phosphonic acid esters are used for the preparation of linear poly(phosphonate)s via ringopening polymerization resulting in polymers with a hydrolytically stable P-C bond in the polymer backbone. Phostones have the stable P-C-bond within the cycle, which leads to a dramatic increase of the monomer stability towards hydrolysis and long shelf-lives compared to other cyclic phosphoesters, which hydrolyze immediately at contact with water. Two phostone-monomers containing ethoxy or butoxy pendant chains were prepared in a single step synthesis from inexpensive starting materials avoiding the usage of SOCl2 or POCl3. Polymers with ethoxy side chains are water-soluble without a lower critical solution temperature, nontoxic to murine macrophages, and hydrolytically degradable under basic conditions. The polymerization kinetics for different catalyst systems were evaluated for both monomers in order to identify optimal polymerization conditions, resulting in polyphosphonates with molecular weights between 3000 and 25100 g/mol with reasonable molecular weight dispersities (<1.6). Due to the ease of synthesis and distinct different hydrolysis kinetics compared to side-chain polyphosphonates, we believe that these new polyphostones represent a valuable addition to water-soluble biopolymers for future biomedical applications.

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A Ring-Closing Metathesis Strategy to Phosphonosugars

Cited by 41 publications

References 33 publications

Recent developments in entropy‐driven ring‐opening metathesis polymerization: Mechanistic considerations, unique functionality, and sequence control

Recent developments in entropy‐driven ring‐opening metathesis polymerization: Mechanistic considerations, unique functionality, and sequence control

Ring Closing Metathesis in the Synthesis of Biologically Interesting Peptidomimetics, Sugars and Alkaloids

Polymerizing Phostones: A Fast Way to In-Chain Poly(phosphonate)s with Adjustable Hydrophilicity

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