Multistereocenter-Containing Cyclopentanoids from Ynamides via Oxazolidinone-Controlled Nazarov Cyclization

The Journal of Organic Chemistry
Narasimhulu ManchalaBernard L Flynn

Abstract

Achieving ready-enantioselective access to multistereocenter-containing cyclopentyl rings is an area of great significance to organic synthesis. In this work, we describe a general protocol for accessing multistereocenter-containing cyclopentanoids from simple N-alkynyloxazolidinones (Ox-ynamides). This protocol involves conversion of Ox-ynamides into Ox-activated divinyl and aryl vinyl ketones that undergo facile Nazarov cyclization with excellent chemo-, regio-, and stereocontrol. The Ox auxiliary directs all aspects of reactivity and selectivity, both in the electrocyclization and in the subsequent transformations of the resulting oxyallyl intermediate. Stereoinduction in the electrocyclization results from a "coupled-torque" mechanism in which rotation of the Ox group, driven by increasing orbital overlap of the nitrogen lone pair with the incipient oxyallyl cation, is coupled with the rotation of the termini of the pentadienyl cation, favoring a particular direction of conrotatory ring closure (torquoselectivity). The associated lone-pair stabilization of the transition state by Ox promotes cyclization of traditionally resistant substrates, broadening the scope of this asymmetric Nazarov cyclization. The Ox group also faci...Continue Reading

References

Apr 16, 2003·Accounts of Chemical Research·Marcus A Tius
Jul 5, 2003·Chemical Communications : Chem Comm·Daniel J KerrBernard L Flynn
Nov 20, 2003·Journal of the American Chemical Society·Wei HeAlison J Frontier
Nov 17, 2006·Organic Letters·John A MalonaAlison J Frontier
Dec 29, 2007·Journal of the American Chemical Society·Wei HeAlison J Frontier
Sep 24, 2009·Chemical Communications : Chem Comm·Tina N GrantFrederick G West
Oct 16, 2009·Journal of Medicinal Chemistry·Frank LoveringChristine Humblet
Sep 30, 2010·The Journal of Organic Chemistry·Daniel J KerrBernard L Flynn
Aug 23, 2011·Tetrahedron·Naoyuki ShimadaMarcus A Tius
Mar 30, 2012·Organic Letters·Daniel J KerrBernard L Flynn
Apr 5, 2012·Journal of the American Chemical Society·David LebœufAlison J Frontier
Jun 14, 2013·Journal of the American Chemical Society·Bernard L FlynnElizabeth H Krenske
Jul 5, 2013·Angewandte Chemie·Yonghoon KwonFrederick G West
Nov 8, 2013·Chemical Society Reviews·Marcus A Tius
May 20, 2015·The Journal of Organic Chemistry·François M LeFortD Jean Burnell
Jan 21, 2016·Chemistry : a European Journal·Bartolo GabrieleLucia Veltri
Apr 22, 2016·Chemical Reviews·Svilen P SimeonovCarlos A M Afonso

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Citations

Oct 20, 2020·Chemical Society Reviews·Ciarán C LynchChristian Wolf

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