Diverse Natural Products from Dichlorocyclobutanones: An Evolutionary Tale

Accounts of Chemical Research
Jean-Pierre DeprésAndrew E Greene

Abstract

11-Nor PGE2 was prepared in our laboratory several years ago and used to obtain the corresponding ring-expanded γ-butyrolactam, γ-butyrolactone, and cyclopentanone derivatives. The conversion of a cyclobutanone into a cyclopentanone had relatively little precedent and merited further study. It was soon found that the presence of a single chlorine adjacent to the carbonyl not only greatly accelerated the reaction with ethereal diazomethane, but also substantially enhanced its regioselectivity; not surprisingly, a second chlorine further increased both. The confluence of this finding and the discovery by Krepski and Hassner that the presence of phosphorus oxychloride significantly improved the Zn-mediated dehalogenation procedure for the preparation of α,α-dichlorocyclobutanones from olefins provided the starting point for decades' worth of exciting adventures in natural product synthesis. A wide variety of naturally occurring 5-membered carbocycles (e.g., hirsutanes, cuparenones, bakkanes, guaianolides, azulenes) could thus be prepared by using dichloroketene-olefin cycloaddition, followed by regioselective one-carbon ring expansion with diazomethane. Importantly, it was also found that natural γ-butyrolactones (e.g., β-oxygenat...Continue Reading

References

Aug 4, 2001·The Journal of Organic Chemistry·M O RasmussenA E Greene
Apr 10, 2003·Chemical Reviews·Edward Lee-Ruff, Gabriela Mladenova
Jul 14, 2005·Angewandte Chemie·Sébastien CarretJean-Pierre Deprés
Oct 6, 2006·Organic Letters·Julien CecconJean-François Poisson
Aug 7, 2007·Angewandte Chemie·Sébastien Carret, Jean-Pierre Deprés
Feb 6, 2008·Natural Product Reports·Joseph P Michael
Sep 19, 2008·Organic Letters·Benjamin DarsesJean-François Poisson
May 8, 2009·Organic & Biomolecular Chemistry·Julien CecconJean-François Poisson
Aug 21, 2010·Organic Letters·Benjamin DarsesJean-François Poisson
Jan 31, 2012·The Journal of Organic Chemistry·Benjamin DarsesJean-François Poisson
Apr 6, 2013·The Journal of Organic Chemistry·Paidi Venkatram ReddyPhilippe Delair
Aug 27, 2014·Natural Product Reports·Jeremy Robertson, Kiri Stevens
Aug 19, 2015·Organic & Biomolecular Chemistry·Anushree KamathPhilippe Delair

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Citations

Feb 9, 2016·Chemical Reviews·Nuno R CandeiasPedro M P Gois
Jun 22, 2017·The Journal of Organic Chemistry·Hanuman P KalmodeD Srinivasa Reddy
Jan 27, 2019·Chemical Communications : Chem Comm·Panpan WangZhuangzhi Shi
Dec 18, 2020·ChemistryOpen·Stefanie BeckAndreas J Kornath
Mar 12, 2021·Organic Letters·Audrey ViceriatJean-François Poisson
Aug 10, 2018·Journal of the American Chemical Society·Su Yong ShimDo Hyun Ryu
Jul 17, 2018·Organic Letters·Pauline RullièreJean-François Poisson

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