Photochemical Synthesis of Prochiral Dialkyl 3,3-Dialkylcyclopropene-1,2-dicarboxylates with Facial Shielding Substituents and Related Substrates

Hashmi, A. Stephen K.; Grundl, Marc A.; Nass, Andreas Rivas; Naumann, Frank; Bats, Jan W.; Bolte, Michael

doi:10.1002/1099-0690(200112)2001:24<4705::aid-ejoc4705>3.0.co;2-j

Cited by 15 publications

(9 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Spectral data was in accordance with the literature. 56 1 H NMR (CDCl 3 , 400 MHz) δ 4.82 (d, 4H, J = 2.5), 2.57 (t, 2H, J = 2.5). 13 C NMR (CDCl 3 , 100 MHz) δ 150.9, 76.7, 75.8, 74.9, 54.2.…”

Section: Methodsmentioning

confidence: 99%

Thiol-Selective Fluorogenic Probes for Labeling and Release

2009

View full text Add to dashboard Cite

Thiol alkylation is a powerful technique for the labeling of proteins. We report a new class of highly reactive, selective, and fluorogenic probes for thiols in aqueous solution at neutral pH, based on the 7-oxanorbornadiene (OND) framework. The maleate moiety in 7-oxabicyclo[2.2.1]hept-2,5-diene-2,3-dicarboxylic acid esters serves as both a tunable electrophile and an intramolecular quencher of an attached dansyl fluorophore. Thiols have been found to add with high rates (second-order rate constants of 40–200 M−1s−1) to give adducts that exhibit enhancements of fluorescence intensity up to 180-fold. The resulting adducts are also versatile with respect to cleavage (release) reactions by two different mechanisms. First, retro-Diels–Alder fragmentation occurs with half lives from days to weeks at room temperature, and an epoxide derivative is also reported that is incapable of cycloreversion cleavage. Second, monoamide OND derivatives undergo rapid closure to succinimide derivatives upon thiol addition, providing a thiol-triggered mechanism for immediate alcohol release. Peptides and proteins containing free thiol groups were labeled with OND electrophiles with high chemoselectivity. Since the system is so easily assembled from readily accessible modules, various functional groups can be added to OND linkers to allow the attachment of other molecules of interest.

show abstract

Section: Methodsmentioning

confidence: 99%

Thiol-Selective Fluorogenic Probes for Labeling and Release

2009

View full text Add to dashboard Cite

show abstract

“…Alternatively, cyclopropenes were synthesized from EDG-EDG diazo compounds and acetylenedicarboxylates. In the first step, 1,3-dipolar cycloaddition leads to the formation of a five-membered product which photochemically decomposes with nitrogen evolution to give the desired cyclopropene …”

Section: [2+1]-cycloadditionsmentioning

confidence: 99%

Lightening Diazo Compounds?

Durka

Turkowska

Gryko

2021

ACS Sustainable Chem. Eng.

171

View full text Add to dashboard Cite

The development of new sustainable reactions and protocols is essential to fulfill the growing demands of every branch of organic chemistry for greener synthetic methodologies. In this context, the use of visible light as the only source of energy is highly appealing. Since diazo compounds are valuable reagents in organic synthesis, their transformations realized in a sustainable manner are of interest. High reactivity and easy availability make them suitable for solar-driven transformations. Indeed, photochemical reactions of diazo compounds have recently proven a valuable alternative to transition metal catalysis. In this perspective, we highlight applications of these reagents under visible irradiation, particularly focusing on recent advancements. These include photochemical generation of carbenes and radicals which involve many relevant reactions, [2+1]-cycloadditions, X−H and C−H insertions, Wolff rearrangement, and more. Mechanistic aspects of these processes are briefly addressed to give readers a deeper understanding of rules underlying photoreactivity of diazo compounds. We conclude by emphasizing significant advancements and discussing challenges for future developments in the photochemistry of these valuable reagents.

show abstract

“…The bond lengths of C1=N1 [1.288 (1) Å], N1–N2 [1.383 (1) Å], and C11=O1 [1.243 (1) Å] bonds are comparable with those of related structures. 28 − 32 …”

Section: Resultsmentioning

confidence: 99%

Supramolecular Self-Assembly Mediated by Multiple Hydrogen Bonds and the Importance of C–S···N Chalcogen Bonds in N′-(Adamantan-2-ylidene)hydrazide Derivatives

et al. 2022

View full text Add to dashboard Cite

The present article comprehensively examines six N ′-(adamantan-2-ylidene)hydrazide derivatives using the Hirshfeld surface analysis, PIXEL energy for molecular dimers, lattice energies for crystal packing, and topological analysis for intramolecular and intermolecular interactions. The crystal structure of one of the N ′-(adamantan-2-ylidene)hydrazide derivatives, namely, N ′-(adamantan-2-ylidene)-5-bromothiophene-2-carbohydrazide 1 , C 15 H 17 N 2 OSBr, has been determined and analyzed in detail along with five closely related structures. The molecular conformation of 1 is locked by an intramolecular C–S···N chalcogen bond as found in one of its closely related structure, namely, N ′-(adamantan-2-ylidene)thiophene-2-carbohydrazide. Furthermore, a detailed potential energy surface scan analysis has been performed to highlight the importance of a chalcogen bond. Two of these compounds possess syn-orientation for amide units, whereas the corresponding moiety exhibits anti-conformations in the remaining four structures. The Hirshfeld surface and its decomposed fingerprint plots provide a qualitative picture of acyl substituent effects on the intermolecular interactions toward crystal packing of these six structures. Intermolecular interaction energies for dimers observed in these structures calculated by density functional theory (B97D3/def2-TZVP) and PIXEL (MP2/6-31G**) methods are comparable. This study also identifies that multiple hydrogen bonds, including N/C–H···O/N and C–H···π interactions, are collectively responsible for a self-assembled synthon. The nature and strength of these interactions have been studied using atoms in molecule topological analysis. The in vitro antiproliferative activity of compound 1 was assessed against five human tumor cell lines and showed marked antiproliferative activity.

show abstract

Photochemical Synthesis of Prochiral Dialkyl 3,3-Dialkylcyclopropene-1,2-dicarboxylates with Facial Shielding Substituents and Related Substrates

Cited by 15 publications

References 14 publications

Thiol-Selective Fluorogenic Probes for Labeling and Release

Thiol-Selective Fluorogenic Probes for Labeling and Release

Lightening Diazo Compounds?

Supramolecular Self-Assembly Mediated by Multiple Hydrogen Bonds and the Importance of C–S···N Chalcogen Bonds in N′-(Adamantan-2-ylidene)hydrazide Derivatives

Contact Info

Product

Resources

About