Direct organocatalytic asymmetric heterodomino reactions: the Knoevenagel/Diels-Alder/epimerization sequence for the highly diastereoselective synthesis of symmetrical and nonsymmetrical synthons of benzoannelated centropolyquinanes

The Journal of Organic Chemistry
Dhevalapally B RamacharyCarlos F Barbas

Abstract

Amino acids and amines have been used to catalyze three component hetero-domino Knoevenagel/Diels-Alder/epimerization reactions of readily available various precursor enones (1a-l), aldehydes (2a-p), and 1,3-indandione (3). The reaction provided excellent yields of highly substituted, symmetrical and nonsymmetrical spiro[cyclohexane-1,2'-indan]-1',3',4-triones (5) in a highly diastereoselective fashion with low to moderate enantioselectivity. The Knoevenagel condensation of arylaldehydes (2a-p) and 1,3-indandione (3) under organocatalysis provided arylidene-1,3-indandiones (17) in very good yields. We demonstrate for the first time amino acid- and amine-catalyzed epimerization reactions of trans-spiranes (6) to cis-spiranes (5). The mechanism of conversion of trans-spiranes (6) to cis-spiranes 5 was shown to proceed through a retro-Michael/Michael reaction rather than deprotonation/reprotonation by isolation of the morpholine enamine intermediate of cis-spirane (22). Prochiral cis-spiranes (5ab) and trans-spiranes (6ab) are excellent starting materials for the synthesis of benzoannelated centropolyquinanes. Under amino acid and amine catalysis, the topologically interesting dispirane 24 was prepared in moderate yields. Organoca...Continue Reading

References

Jan 1, 1968·Pure and Applied Chemistry. Chimie Pure Et Appliquée·R B Woodward
Nov 9, 2001·Organic Letters·J M Betancort, C F Barbas
Jan 5, 2002·The Journal of Organic Chemistry·Armando CórdovaCarlos F Barbas
Feb 1, 1996·Chemical Reviews·Lutz F. Tietze
Feb 28, 2002·Journal of the American Chemical Society·Armando CórdovaCarlos F Barbas
Feb 28, 2002·Journal of the American Chemical Society·Armando CórdovaCarlos F Barbas
Mar 14, 2002·Journal of the American Chemical Society·Alan B Northrup, David W C MacMillan
May 16, 2002·Journal of the American Chemical Society·Benjamin List
Jun 13, 2002·Journal of the American Chemical Society·Alan B Northrup, David W C MacMillan
Jul 4, 2002·Journal of the American Chemical Society·Nick A Paras, David W C MacMillan
Jul 18, 2002·Chemical Communications : Chem Comm·Anders BøgevigKarl Anker Jørgensen
Apr 17, 2003·Angewandte Chemie·Karsten Juhl, Karl Anker Jørgensen
Apr 22, 2003·Chemical Communications : Chem Comm·Julie L CavillNicholas C O Tomkinson
May 2, 2003·Journal of the American Chemical Society·Zhuo TangYun-Dong Wu
May 24, 2003·The Journal of Organic Chemistry·Paolo Melchiorre, Karl Anker Jørgensen
Jun 24, 2003·Angewandte Chemie·Chandrakala PidathalaBenjamin List
Jul 5, 2003·Organic Letters·Olivier AndreyGérald Bernardinelli
Sep 4, 2003·Journal of the American Chemical Society·Sean P BrownDavid W C MacMillan
Dec 6, 2003·The Journal of Organic Chemistry·Wolfgang NotzCarlos F Barbas

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Citations

Jan 18, 2016·European Journal of Medicinal Chemistry·Khaled M DarwishMohamed A Helal
May 11, 2015·Molecular Diversity·Shima Asadi, Ghodsi Mohammadi Ziarani
May 17, 2011·Acta Biomaterialia·Boaz MizrahiDaniel S Kohane
Feb 19, 2005·Angewandte Chemie·Diego J Ramón, Miguel Yus
Nov 3, 2016·Chemical Society Reviews·Vanesa Marcos, José Alemán
Sep 27, 2018·Organic & Biomolecular Chemistry·Han XuXin-Yan Wu
Feb 3, 2007·Organic & Biomolecular Chemistry·Dhevalapally B Ramachary, G Babul Reddy
Jan 17, 2007·Angewandte Chemie·Dieter EndersMatthias R M Hüttl
Feb 1, 2008·Angewandte Chemie·Scott E Denmark, Gregory L Beutner
Apr 19, 2008·Angewandte Chemie·Alessandro Dondoni, Alessandro Massi
Jun 6, 2008·Organic & Biomolecular Chemistry·Xinhong Yu, Wei Wang
Aug 14, 2009·Organic & Biomolecular Chemistry·Dhevalapally B RamacharyKinthada Ramakumar
Apr 25, 2006·Organic & Biomolecular Chemistry·Dhevalapally B RamacharyG Babul Reddy
Jul 31, 2008·Angewandte Chemie·Paolo MelchiorreGiuseppe Bartoli
Sep 15, 2011·Organic & Biomolecular Chemistry·Dhevalapally B RamacharySharmistha Banerjee
Mar 1, 2012·Chemistry : a European Journal·Matthew N PennellTom D Sheppard
Jan 13, 2010·Organic & Biomolecular Chemistry·Dhevalapally B RamacharyChintalapudi Venkaiah
Jan 16, 2018·Chemical Communications : Chem Comm·Qian-Qian YangYing-Chun Chen

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