DNA-Templated [2+2] Photocycloaddition: A Straightforward Entry into the Aplysinopsin Family of Natural Products.
Angew Chem Int Ed Engl
; 57(36): 11786-11791, 2018 09 03.
Article
en En
| MEDLINE
| ID: mdl-29989287
ABSTRACT
Biosynthetic considerations inspired us to harness the templating properties offered by DNA to promote a [2+2] photoinduced cycloaddition. The method was developed based on the dimerization of (E)-aplysinopsin, which was previously shown to be unproductive in solution. In sharp contrast, exposure of this tryptophan-derived olefin to light in the presence of salmon testes DNA (st-DNA) reproducibly afforded the corresponding homo-dimerized spiro-fused cyclobutane in excellent yields. DNA provides unique templating interactions enabling a singular mimic of the solid-state aggregation necessary for the [2+2] photocycloaddition to occur. This method was ultimately used to promote the prerequisite dimerizations leading to both dictazoleâ
B and tubastrindoleâ
B, thus constituting the first example of a DNA-mediated transformation to be applied to the total synthesis of a natural product.
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2018
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Article