A Concise Total Synthesis of (+)‐Waihoensene Guided by Quaternary Center Analysis. Issue 32 (3rd June 2020)

• Record Type: Journal Article
• Authors: Peng, Cheng; Arya, Piyush; Zhou, Zhiyao; Snyder, Scott A.
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 32(2020)
• Page Start: 13521
• Page End: 13525
• Publication Date: 2020-06-03
• Subjects: Conia-ene -- Pauson–Khand -- total synthesis -- triquinanes -- waihoensene; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202004177
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The four contiguous all‐carbon quaternary centers of waihoensene, coupled with the absence of any traditional reactive functional groups other than a single alkene, render it a particularly challenging synthetic target among angular triquinane natural products. Here, we show that its polycyclic frame can be assembled concisely by using a strategically chosen quaternary center to guide the formation of the other three through judiciously selected C−C bond formation reactions. Those events, which included a unique Conia‐ene cyclization and a challenging Pauson–Khand reaction, afforded a 17‐step synthesis of the molecule in enantioenriched form. Abstract : The preparation of unique, non‐functionalized terpenes remains challenging. The strategic use of a minimal number of functional groups, coupled with retrosynthetic planning based on the use of a guiding all‐carbon quaternary center to forge three additional such centers, fueled by some unique C−C bond forming steps, can afford an expeditious, 17‐step total synthesis of the unique angular triquinane natural product (+)‐waihoensene.