Enantiospecific Total Synthesis of the Highly Strained (−)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization

Enantiospecific Total Synthesis of the Highly Strained (−)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization

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 patt...

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Veröffentlicht in:Journal of the American Chemical Society 2017-04, Vol.139 (14), p.5007-5010
Hauptverfasser: Hu, Pengfei, Snyder, Scott A
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Snyder, Scott A
description 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.
doi_str_mv 10.1021/jacs.7b01454
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title Enantiospecific Total Synthesis of the Highly Strained (−)-Presilphiperfolan-8-ol via a Pd-Catalyzed Tandem Cyclization
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