Method for a Convenient and Efficient Synthesis of Amino Acid Acrylic Monomers with Zwitterionic Structure

Nagaoka, Shoji; Shundo, Atsuomi; Satoh, Takao; Nagira, Kazuhiko; Kishi, Ryoichi; Ueno, Katsuhiko; Iio, Katsunori; Ihara, Hirotaka

doi:10.1080/00397910500212932

Cited by 27 publications

(21 citation statements)

References 5 publications

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“…Yet again, the application of the acidic O -acylation methodology within such a specialized field as dental materials has perhaps rendered the work rather opaque to materials scientists in general. This is unfortunate, as use of the mostly outdated and cumbersome copper protective chemistry has continued to dominate in the literature for the preparation of side-chain acrylic derivatives of hydroxyamino acids [ 5 – 8 ].…”

Section: Reviewmentioning

confidence: 99%

“…The side-chain-acylated lysine can then be liberated by decomposition of the copper salt with hydrogen sulfide. This methodology has subsequently been employed in a more generic sense as a preparative method for synthesis of acrylic side-chain derivatives of amino acids such as lysine, ornithine, tyrosine and serine [ 6 – 8 ], having modified the original technique by liberating the acylated derivative from its copper salt using 8-hydroxyquinoline as an organic chelating precipitant [ 8 ].…”

Section: Introductionmentioning

confidence: 99%

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Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Kristensen¹

2015

Beilstein J. Org. Chem.

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SummaryAmino acids, whether natural, semisynthetic or synthetic, are among the most important and useful chiral building blocks available for organic chemical synthesis. In principle, they can function as inexpensive, chiral and densely functionalized starting materials. On the other hand, the use of amino acid starting materials routinely necessitates protective group chemistry, and in reality, large-scale preparations of even the simplest side-chain derivatives of many amino acids often become annoyingly strenuous due to the necessity of employing protecting groups, on one or more of the amino acid functionalities, during the synthetic sequence. However, in the case of hydroxyamino acids such as hydroxyproline, serine, threonine, tyrosine and 3,4-dihydroxyphenylalanine (DOPA), many O-acyl side-chain derivatives are directly accessible via a particularly expedient and scalable method not commonly applied until recently. Direct acylation of unprotected hydroxyamino acids with acyl halides or carboxylic anhydrides under appropriately acidic reaction conditions renders possible chemoselective O-acylation, furnishing the corresponding side-chain esters directly, on multigram-scale, in a single step, and without chromatographic purification. Assuming a certain degree of stability under acidic reaction conditions, the method is also applicable for a number of related compounds, such as various amino alcohols and the thiol-functional amino acid cysteine. While the basic methodology underlying this approach has been known for decades, it has evolved through recent developments connected to amino acid-derived chiral organocatalysts to become a more widely recognized procedure for large-scale preparation of many useful side-chain derivatives of hydroxyamino acids and related compounds. Such derivatives are useful in peptide chemistry and drug development, as amino acid amphiphiles for asymmetric catalysis, and as amino acid acrylic precursors for preparation of catalytically active macromolecular networks in the form of soluble polymers, crosslinked polymer beads or nanoparticulate systems. The objective of the present review is to increase awareness of the existence and convenience of this methodology, assess its competitiveness compared to newer and more elaborate procedures for chemoselective O-acylation reactions, spur its further development, and finally to chronicle the informative, but poorly documented history of its development.

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Section: Reviewmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Kristensen¹

2015

Beilstein J. Org. Chem.

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“…[25] This is a useful strategy for lysine and serine, both of which can compete with the a-amine in coupling reactions or in reactions with acyl chlorides. The copper is easily removed with 8-hydroxyquinoline, which has higher binding affinity for the metal ion.…”

Section: Functional Site 3: the R Groupmentioning

confidence: 99%

“…The copper is easily removed with 8-hydroxyquinoline, which has higher binding affinity for the metal ion. This strategy (Scheme 4), based on Kurtz's work in 1941, [26] has been used to synthesize methacrylate monomers made from lysine, [27][28][29] serine, [30] tyrosine, orthinine, [25,31] and hydroxyproline. [32] Thia-Michael addition chemistry has been used by the groups of Leggett and Armes to synthesize a zwitterionic monomer from methacrylate-acrylate precursor (3-acryloxy)-2-hydroxypropyl methacrylate) and cysteine (Scheme 5).…”

Section: Functional Site 3: the R Groupmentioning

confidence: 99%

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Amino Acid Functional Polymers: Biomimetic Polymer Design Enabling Catalysis, Chiral Materials, and Drug Delivery

2016

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Amino acids are the natural building blocks for the world around us. Highly functional, these small molecules have unique catalytic properties, chirality, and biocompatibility. Imparting these properties to surfaces and other macromolecules is highly sought after and represents a fast-growing field. Polymers functionalized with amino acids in the side chains have tunable optical properties, pH responsiveness, biocompatibility, structure and self-assembly properties. Herein, we review the synthesis of amino acid functional polymers, discuss manipulation of available strategies to achieve the desired responsive materials, and summarize some exciting applications in catalysis, chiral particles, and drug delivery.

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8-Hydroxyquinoline

Ferreira¹

2013

Encyclopedia of Reagents for Organic Synthesis

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Method for a Convenient and Efficient Synthesis of Amino Acid Acrylic Monomers with Zwitterionic Structure

Cited by 27 publications

References 5 publications

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Chemoselective O-acylation of hydroxyamino acids and amino alcohols under acidic reaction conditions: History, scope and applications

Amino Acid Functional Polymers: Biomimetic Polymer Design Enabling Catalysis, Chiral Materials, and Drug Delivery

8-Hydroxyquinoline

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