Photochemical Formation of Dibenzosilacyclohept-4-yne for Cu-Free Click Chemistry with Azides and 1,2,4,5-Tetrazines
| Authors | |
|---|---|
| Year of publication | 2016 |
| Type | Article in Periodical |
| Magazine / Source | Organic Letters |
| MU Faculty or unit | |
| Citation | |
| Web | http://pubs.acs.org/doi/abs/10.1021/acs.orglett.6b02367 |
| Doi | http://dx.doi.org/10.1021/acs.orglett.6b02367 |
| Field | Organic chemistry |
| Keywords | DIELS-ALDER REACTIONS; CYCLOADDITION REACTIONS; BIOORTHOGONAL REACTIONS; LIVING CELLS; GENERATION; REACTIVITY; SIEBENRINGSYSTEMEN; BIOCONJUGATION; CYCLOHEPTYNES; BIOMOLECULES |
| Description | Photochemical generation of dibeniOsilacyclohept-4-yne 3 from the corresponding, cydopropenone 1 and its copper-free click reactions are reported. Steady-state irradiation, kinetic, and- transient absorption spectroscopy studies revealed that strained alkyne 3 is rapidly (<5 ns) and efficiently (Phi = 0.58-0.71) photoreleased from 1 and undergoes remarkably fast, selective, and high-yielding 1,3-dipolar cycloaddition with benzyl azide (similar to 20 M-1 s(-1)) or [4 + 2] inverse electron-demand Diels Alder reaction with 1,2,4,5-tetrazines (similar to 260 M-1 s(-1)) in both methanol and acetonitrile. |
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