Mechanistic investigation and further optimization of the aqueous Glaser−Hay bioconjugation

Travis, Christopher R.; Mazur, Lauren E; Peairs, Emily M.; Gaunt, Gillian H.; Young, Douglas D.

doi:10.1039/c9ob00327d

Cited by 6 publications

(11 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…By considering that these methods efficiently provide strained macrocyclic structures, two alkyne moieties require nonlinear conformation in the intermediate for the reductive elimination step (Figure b). The mechanistic study of Glaser coupling is still ongoing experimentally and theoretically . These studies suggest that the proposed intermediates I – IV depend on the valence at the copper metals.…”

Section: Synthetic Methods For π‐Conjugated Macrocycles Containing Anmentioning

confidence: 99%

“…The mechanistic study of Glaser coupling is still ongoing experimentally [55] and theoretically. [56][57][58][59][60] These studies suggest that the proposed intermediates I-IV depend on the valence at the copper metals. Researchersh ave to pay attention to the copperp recatalyst used, which may affect the efficiency of macrocyclization.…”

Section: Synthetic Methodsf or P-conjugated Macrocycles Containing Anmentioning

confidence: 99%

“…The association constant (K a )w as roughlye stimated at more than 5.0 10 6 m À1 by NMR measurements, which was larger than for the 33 c'C 60 complex. This resulta lso supports the notion that the introductiono fp olyaromatics in CPPAs enhances the C 60 encapsulation ability.T he electron-rich [6]CPPAd erivative 49 also acts as ag ood host molecule for C 60 . Based on the high encapsulation ability of anthracene-containingC PPAd erivatives, Miki, Ohe, and coworkers demonstrated the synthesis of twin [6]CPPA derivatives, in which two [6]CPPAs are hingedb y one benzene ring, and its encapsulation of two C 60 molecules (Figure 25 b).…”

Section: Synthesis Of Cppas and Their Supramolecular Chemistrymentioning

confidence: 99%

“…Based on the high encapsulation ability of anthracene-containingC PPAd erivatives, Miki, Ohe, and coworkers demonstrated the synthesis of twin [6]CPPA derivatives, in which two [6]CPPAs are hingedb y one benzene ring, and its encapsulation of two C 60 molecules (Figure 25 b). [119] The precursors 55 and 56 were synthesized by stepwise cross-coupling of 52 with dihydroanthracene 53 or 54.T he precursor 55 60 to give the twin [6]CPPA-fullerene 1:2c omplex (57'2C 60 ), which wasd etected by MALDI-TOFm ass spectrometry.A fter forming 57'C 60 ,t he electron density of the host [6]CPPAi sd ecreased by charge-transfer interaction. The second complexation afforded unstable 1:2c omplex 57'2C 60 , which decomposedd uring purification.…”

Section: Synthesis Of Cppas and Their Supramolecular Chemistrymentioning

confidence: 99%

See 3 more Smart Citations

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

Miki

Ohe

2019

Chemistry A European J

View full text Add to dashboard Cite

Angle‐strained alkyne‐containing π‐conjugated macrocycles are attractive compounds both in functional materials chemistry and biochemistry. Their interesting reactivity as well as photophysical and supramolecular properties have been revealed in the past three decades. This review highlights the recent advances in angle‐strained alkyne‐containing π‐conjugated macrocycles, especially their synthetic methods, the bond angles of alkynes (∠sp at C≡C−C), and their functions. The theoretical and experimental research on cyclo[n]carbons and para‐cyclophynes consisting of ethynylenes and para‐phenylenes are mainly summarized. Related macrocycles bearing other linkers, such as ortho‐phenylenes, meta‐phenylenes, heteroaromatics, biphenyls, extended aromatics, are also overviewed. Bond angles of strained alkynes in π‐conjugated macrocycles, which are generable, detectable, and isolable, are summarized at the end of this review.

show abstract

Section: Synthetic Methods For π‐Conjugated Macrocycles Containing Anmentioning

confidence: 99%

Section: Synthetic Methodsf or P-conjugated Macrocycles Containing Anmentioning

confidence: 99%

Section: Synthesis Of Cppas and Their Supramolecular Chemistrymentioning

confidence: 99%

Section: Synthesis Of Cppas and Their Supramolecular Chemistrymentioning

confidence: 99%

See 2 more Smart Citations

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

Miki

Ohe

2019

Chemistry A European J

View full text Add to dashboard Cite

show abstract

“…One common bioorthogonal reaction employed to prepare protein bioconjugates is the copper‐catalyzed azide/alkyne cycloaddition (CuAAC), known as the “copper click” reaction, in which an UAA with either an alkyne or azide group is reacted with an azide‐containing or alkyne‐containing reaction partner, respectively . More recently, we reported the development of a Glaser–Hay bioconjugation reaction involving the coupling of an alkynyl UAA with a terminal alkyne reaction partner to afford a covalent diyne linkage . However, there are a limited number of bioconjugation reactions available, as they necessitate physiological conditions and must lack cross‐reactivity with endogenous biological systems .…”

Section: Figurementioning

confidence: 99%

Genetic Encoding of a Bioconjugation Handle for [2+2+2] Cycloaddition Reactions

et al. 2019

Self Cite

View full text Add to dashboard Cite

Protein bioconjugates have many criticala pplications, especially in the development of therapeutics. Consequently,t he design of novel methodologies to prepare protein bioconjugates is of great importance.H erein we presentt he development and optimization of an ovel strategy to prepare bioconjugates through ag enetically encoded [2+ +2+ +2] cycloaddition reaction. To do this, an ovel unnaturala minoa cid (UAA) containing ad ipropargyl amine functionality was synthesized and incorporated site specifically.T his UAA-containing protein was reactedw ith an alkyne-containing fluorophore to afford ac ovalentlyl inked, well-definedp rotein bioconjugate. This reaction is convenient with an optimized reactiont ime of just two hours at room temperature and yields as table, polysubstituted benzene ring. Overall, this work contributes an ew bioconjugation strategy to the growingt oolbox of reactions to develop protein bioconjugates, which have am yriad of applications.

show abstract

Using Experimental Spectroscopic Data to Guide and Validate Mechanisms in Catalyzed Aldol Reactions

2022

View full text Add to dashboard Cite

Organic chemistry students often struggle with reaction mechanisms, particularly in how they are proposed and justified. In this activity targeting second year organic undergraduates, students used infrared spectroscopy (IR) to track the reaction progress of two distinct aldol reactions and used polarimetry to analyze the stereoselectivity of aldol catalysts. Students worked in two pairs, with one focusing on the traditional hydroxide-catalyzed aldol reaction (two units of propionaldehyde combining via an enolate intermediate) and the other focusing on the enantioselective L-proline-catalyzed aldol reaction (propionaldehyde catalyzed by Lproline, showing an iminium intermediate). During the course of the lab period, students used IR spectra showing kinetic data and guided questions to propose and validate the reaction mechanisms. After the pairs of students analyzed their individual reactions, they formed groups of four to further analyze and compare the two mechanisms. This comparison of IR and polarimetry data allowed students to discuss both pathways and consider why chemists use different reaction conditions to reach the same product. The focus of this experiment is to improve the understanding of reaction mechanisms and the process by which scientists propose and justify mechanisms, while giving students practical experience with IR spectroscopy, polarimetry, and intermediate analysis.

show abstract

Mechanistic investigation and further optimization of the aqueous Glaser−Hay bioconjugation

Abstract: The Glaser–Hay bioconjugation has emerged as an efficient method to generate bioconjugates with therapeutic applications.

Cited by 6 publications

References 34 publications

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

π‐Conjugated Macrocycles Bearing Angle‐Strained Alkynes

Genetic Encoding of a Bioconjugation Handle for [2+2+2] Cycloaddition Reactions

Using Experimental Spectroscopic Data to Guide and Validate Mechanisms in Catalyzed Aldol Reactions

Contact Info

Product

Resources

About