Regio- and Stereo-Selective Isomerization of Borylated 1,3-Dienes Enabled by Selective Energy Transfer Catalysis.
Angew Chem Int Ed Engl
; 63(22): e202404233, 2024 May 27.
Article
in En
| MEDLINE
| ID: mdl-38545942
ABSTRACT
Configurationally-defined dienes are pervasive across the bioactive natural product spectrum, where they typically manifest themselves as sorbic acid-based fragments. These C5 motifs reflect the biosynthesis algorithms that facilitate their construction. To complement established biosynthetic paradigms, a chemical platform to facilitate the construction of stereochemically defined, functionalizable dienes by light-enabled isomerization has been devised. Enabled by selective energy transfer catalysis, a variety of substituted ß-boryl sorbic acid derivatives can be isomerized in a regio- and stereo-selective manner (up to 97 3). Directionality is guided by a stabilizing nOâpB interaction in the product this constitutes a formal anti-hydroboration of the starting alkyne. This operationally simple reaction employs low catalyst loadings (1â
mol %) and is complete in 1â
h. X-ray analysis supports the hypothesis that the nOâpB interaction leads to chromophore bifurcation this provides a structural foundation for selective energy transfer.
Full text:
1
Database:
MEDLINE
Language:
En
Journal:
Angew Chem Int Ed Engl
/
Angew. Chem. (Int. ed., Internet)
/
Angewandte Chemie (International ed. Internet)
Year:
2024
Type:
Article
Affiliation country:
Germany