Unknown

Dataset Information

0

1,3-Dipolar Cycloaddition with Diazo Groups: Noncovalent Interactions Overwhelm Strain.

ABSTRACT: Like azides, diazoacetamides undergo 1,3-dipolar cycloadditions with oxanorbornadienes (OND) in a reaction that is accelerated by the relief of strain in the transition state. The cycloaddition of a diazoacetamide with unstrained ethyl 4,4,4-trifluoro-2-butynoate is, however, 35-fold faster than with the analogous OND because of favorable interactions with the fluoro groups. Its rate constant (k = 0.53 M(-1) s(-1) in methanol) is comparable to those of strain-promoted azide-cyclooctyne cycloadditions.

SUBMITTER: Gold B 

PROVIDER: S-EPMC5148626 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

1,3-Dipolar Cycloaddition with Diazo Groups: Noncovalent Interactions Overwhelm Strain.

Gold Brian B   Aronoff Matthew R MR   Raines Ronald T RT  

Organic letters 20160906 18

Like azides, diazoacetamides undergo 1,3-dipolar cycloadditions with oxanorbornadienes (OND) in a reaction that is accelerated by the relief of strain in the transition state. The cycloaddition of a diazoacetamide with unstrained ethyl 4,4,4-trifluoro-2-butynoate is, however, 35-fold faster than with the analogous OND because of favorable interactions with the fluoro groups. Its rate constant (k = 0.53 M(-1) s(-1) in methanol) is comparable to those of strain-promoted azide-cyclooctyne cycloaddi  ...[more]

Similar Datasets

Unknown Diazo Compounds as Highly Tunable Reactants in 1,3-Dipolar Cycloaddition Reactions with Cycloalkynes().
| S-EPMC3513925 | biostudies-literature
Unknown Decreasing Distortion Energies without Strain: Diazo-Selective 1,3-Dipolar Cycloadditions.
| S-EPMC5141247 | biostudies-literature
Unknown Bioorthogonal prodrug activation driven by a strain-promoted 1,3-dipolar cycloaddition.
| S-EPMC5811098 | biostudies-literature
Unknown 1,3-Dipolar Cycloadditions of Diazo Compounds in the Presence of Azides.
| S-EPMC5141246 | biostudies-literature
Unknown Isoxazolodihydropyridinones: 1,3-dipolar cycloaddition of nitrile oxides onto 2,4-dioxopiperidines.
| S-EPMC3345193 | biostudies-literature
Unknown Intramolecular diels-alder/1,3-dipolar cycloaddition cascade of 1,3,4-oxadiazoles.
| S-EPMC2587417 | biostudies-literature
Unknown New cofactor supports ?,?-unsaturated acid decarboxylation via 1,3-dipolar cycloaddition.
| S-EPMC4988494 | biostudies-literature
Unknown Synthesis of demissidine by a ring fragmentation 1,3-dipolar cycloaddition approach.
| S-EPMC3671602 | biostudies-literature
Unknown Synthesis of functionalized organotrifluoroborates via the 1,3-dipolar cycloaddition of azides.
| S-EPMC2515368 | biostudies-literature
Unknown Additive-assisted regioselective 1,3-dipolar cycloaddition of azomethine ylides with benzylideneacetone.
| S-EPMC3943969 | biostudies-literature