title: Enantiospecific Total Synthesis of the Highly Strained (-)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization.
abstract: A rare element of high strain in molecules of natural origin is a 1,2-trans fusion of 5-membered rings within a [3.3.0]-bicycle, a motif present in (-)-presilphiperfolan-8-ol. This molecule also possesses a 1,3-trans stereochemical arrangement of substituents on one of its 5-membered rings, a pattern shared by a number of other terpenes. Herein, we disclose the first total synthesis of this highly strained target in 13 steps. The key operation is a Pd-catalyzed tandem cyclization that directly establishes the requisite 1,3-trans stereochemical arrangement on one ring while concurrently setting the stage for the controlled generation of the highly strained 1,2-trans ring fusion of the final architecture.
authors.affiliation: Department of Chemistry, The Scripps Research Institute , 130 Scripps Way, Jupiter, Florida 33458, United States.|Department of Chemistry, University of Chicago , 5735 South Ellis Avenue, Chicago, Illinois 60637, United States.
authors.forename: Pengfei
authors.identifier: http://orcid.org/0000-0003-2915-4102
authors.initials: P
authors.lastname: Hu
authors.affiliation: Department of Chemistry, The Scripps Research Institute , 130 Scripps Way, Jupiter, Florida 33458, United States.|Department of Chemistry, University of Chicago , 5735 South Ellis Avenue, Chicago, Illinois 60637, United States.
authors.forename: Scott A
authors.identifier: http://orcid.org/0000-0003-3594-8769
authors.initials: SA
authors.lastname: Snyder