Affiliation:
1. Department of Chemistry Johns Hopkins University 3400N. Charles St Baltimore MD 21218 USA
2. Department of Chemistry and Biochemistry Messiah University One University Avenue Mechanicsburg PA 17055 USA
3. Department of Chemistry Brock University St. Catharines Ontario L2S3A1 Canada
Abstract
AbstractComplex natural product functionalizations generally involve the use of highly engineered reagents, catalysts, or enzymes to react exclusively at a desired site through lowering of a select transition state energy. In this communication, we report a new, complementary strategy in which all transition states representing undesirable sites in a complex ionophore substrate are simultaneously energetically increased through the chelation of a metal ion to the large fragment we wish to neutralize. In the case of an electrophilic, radical based fluorination reaction, charge repulsion (electric field effects), induced steric effects, and electron withdrawal provide the necessary deactivation and proof of principle to afford a highly desirable natural product derivative. We envisage that many other electrophilic or charge based synthetic methods may be amenable to this approach as well.
Funder
National Science Foundation
Natural Sciences and Engineering Research Council of Canada
Subject
General Chemistry,Catalysis
Cited by
1 articles.
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