DNA-Templated [2+2] Photocycloaddition: A Straightforward Entry into the Aplysinopsin Family of Natural Products.

DNA-Templated [2+2] Photocycloaddition: A Straightforward Entry into the Aplysinopsin Family of Natural Products.
Angew Chem Int Ed Engl. 2018 Jul 10;:
Authors: Duchemin N, Skiredj A, Mansot J, Leblanc K, Vasseur JJ, Beniddir MA, Evanno L, Poupon E, Smietana M, Arseniyadis S
Abstract
Biosynthetic considerations inspired us to harness the template properties offered by DNA to promote a [2+2] photo-induced 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] photo-cycloaddition to occur. This method was ultimately used to promote the prerequisite dimerizations leading to both dictazole B and tubastrindole B, thus constituting the first example of a DNA-mediated transformation to be applied to the total synthesis of a natural product.
PMID: 29989287 [PubMed - as supplied by publisher]

Source: Angewandte Chemie - July 10, 2018 Category: Chemistry Authors: Duchemin N, Skiredj A, Mansot J, Leblanc K, Vasseur JJ, Beniddir MA, Evanno L, Poupon E, Smietana M, Arseniyadis S Tags: Angew Chem Int Ed Engl Source Type: research