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DNA‐Templated [2+2] Photocycloaddition: A Straightforward Entry into the Aplysinopsin Family of Natural Products
Author(s) -
Duchemin Nicolas,
Skiredj Adam,
Mansot Justine,
Leblanc Karine,
Vasseur JeanJacques,
Beniddir Mehdi A.,
Evanno Laurent,
Poupon Erwan,
Smietana Michael,
Arseniyadis Stellios
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201806357
Subject(s) - dna , cyclobutane , cycloaddition , chemistry , olefin fiber , tryptophan , pyrimidine dimer , solid state , natural product , transformation (genetics) , stereochemistry , combinatorial chemistry , dna damage , biochemistry , catalysis , organic chemistry , ring (chemistry) , gene , amino acid
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 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.