Nitrosocarbonyl Hetero-Diels–Alder Cycloaddition: A New Tool for Conjugation

Samoshin, Andrey V.; Hawker, Craig J.; Alaniz, Javier Read de

doi:10.1021/mz500348y

Cited by 32 publications

(26 citation statements)

References 51 publications

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“… 5 However, relatively few small-molecule click reactions perform optimally when used for coupling one macromolecule to another, and often an excess of one coupling partner is required to drive the reaction to completion. 6 There are only a handful of reactions that enable highly efficient macromolecular coupling at equimolarity: the Heck coupling, 7 the nitrile imine-mediated tetrazole-ene cycloaddition reaction, 8 the photoinduced Diels–Alder reaction, 9 the RAFT hetero Diels–Alder reaction, 10 and CuAAC. 11 The development of new click reactions for post-polymerization modification therefore remains an important ongoing challenge in polymer chemistry.…”

Section: Introductionmentioning

confidence: 99%

A New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine–Tertiary Isocyanate Coupling for Polymer Ligation

et al. 2016

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Click reactions have provided access to an array of remarkably complex polymer architectures. However, the term “click” is often applied inaccurately to polymer ligation reactions that fail to respect the criteria that typify a true “click” reaction. With the purpose of providing a universal way to benchmark polymer–polymer coupling efficiency at equimolarity and thus evaluate the fulfilment of click criteria, we report a simple one-pot methodology involving the homodicoupling of α-end-functionalized polymers using a small-molecule bifunctional linker. A combination of SEC analysis and chromatogram deconvolution enables straightforward quantification of the coupling efficiency. We subsequently employ this methodology to evaluate an overlooked candidate for the click reaction family: the addition of primary amines to α-tertiary isocyanates (α-tNCO). Using our bifunctional linker coupling strategy, we show that the amine–tNCO reaction fulfills the criteria for a polymer–polymer click reaction, achieving rapid, chemoselective, and quantitative coupling at room temperature without generating any byproducts. We demonstrate that amine–tNCO coupling is faster and more efficient than the more common amine–tertiary active ester coupling under equivalent conditions. Additionally, we show that the α-tNCO end group is unprecedentedly stable in aqueous media. Thus, we propose that the amine–tNCO ligation is a powerful new click reaction for efficient macromolecular coupling.

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Section: Introductionmentioning

confidence: 99%

A New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine–Tertiary Isocyanate Coupling for Polymer Ligation

et al. 2016

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“…In 2015, the Whiting group reported an extensive study of acylnitroso compounds prepared in situ by the catalytic aerobic oxidation of hydroxycarbamate using CuCl 2 and 2-ethyl-2-oxazoline in methanol [69]. Additionally, acylnitroso compounds can be generated by the rearrangement of diazonitroalkanes 26 [70], the photochemical cleavage of 1,2,4-oxadiazole-4-oxides 25 [71] and the cycloreversion of 9,10-dimethylantracene adducts 27 (Scheme 7) [72–73]. …”

Section: Introductionmentioning

confidence: 99%

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

Brulíková

Harrison

Miller

et al. 2016

Beilstein J. Org. Chem.

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SummaryThe hetero-Diels–Alder reaction between a nitroso dienophile and a conjugated diene to give the 3,6-dihydro-2H-1,2-oxazine scaffold is useful for the synthesis of many biologically interesting molecules due to the diverse opportunities created by subsequent transformations of the resulting 1,2-oxazine ring. This review discusses the rationale for the observed regio- and stereoselectivity and the methods developed in recent years used to control and improve the stereo- and regioselectivity for the synthesis of 1,2-oxazine scaffolds.

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“…图式 11 1,3-环戊二烯与单线态氧气的反应 Scheme 11 Reaction of 1,3-cyclopentadiene with singlet oxygen 环戊二烯的 Diels-Alder 反应的高反应活性使其在有机合成 [69] 、生物分子固定化、热敏聚合物和功能性材料等方面具有广泛的应用 [70,71] . 2015 年, Levandowski…”

Section: 烯炔反应法unclassified

Research Progress on the Synthesis and Application of Cyclopentadiene Derivatives

Ye¹,

Huang²,

Wang³

et al. 2016

Chin. J. Org. Chem.

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Cyclopentadiene and its derivatives are a type of important small molecule cyclic olefin compounds, which have been widely applied in many fields such as synthesis of metallocene compounds, synthesis of organic intermediates and organic photoelectric materials. Based on our recent research results, in this review, the research progress on the synthesis of cyclopentadiene derivatives and the application of some typical cyclopentadiene derivatives in the field of organic synthesis are summarized.

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Nitrosocarbonyl Hetero-Diels–Alder Cycloaddition: A New Tool for Conjugation

Cited by 32 publications

References 51 publications

A New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine–Tertiary Isocyanate Coupling for Polymer Ligation

A New Methodology for Assessing Macromolecular Click Reactions and Its Application to Amine–Tertiary Isocyanate Coupling for Polymer Ligation

Stereo- and regioselectivity of the hetero-Diels–Alder reaction of nitroso derivatives with conjugated dienes

Research Progress on the Synthesis and Application of Cyclopentadiene Derivatives

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