Synergistic Iron-and-Amine Catalysis in Carbocyclizations

Dedicated to Professor Max Malacria on the occasion of his 65^th birthday

Abstract

The fruitful merger of iron catalysis to amine catalysis was successfully applied in the direct intramolecular addition of aldehydes to non-activated alkynes. Accordingly, the carbocyclizations of a range of formyl-alkynes afforded the corresponding cyclopentanes in good to excellent yields. Experimental evidence tends to support a synergistic enamine/π-activation reaction mechanism.

Key words

synergistic catalysis - iron - organocatalysis - carbocyclization - alkenylation

• References


For general reviews on iron-catalysis, see:
• 1a Bolm C, Legros J, Le Paih J, Zani L. Chem. Rev. 2004; 104: 6217
• 1b Correa A, García Mancheño O, Bolm C. Chem. Soc. Rev. 2008; 37: 1108
• 1c Enthaler S, Junge K, Beller M. Angew. Chem. Int. Ed. 2008; 47: 3317
• 1d Iron Catalysis in Organic Chemistry . Plietker B. Wiley-VCH; Weinheim: 2008
• 1e Plietker B. Synlett 2010; 2049
• 1f Sun C.-L, Li B.-J, Shi Z.-J. Chem. Rev. 2011; 111: 1293
• 1g Bézier D, Sortais J.-B, Darcel C. Adv. Synth. Catal. 2013; 355: 19
• 1h Holzwarth MS, Plietker B. ChemCatChem 2013; 5: 1650

For reviews on iron-catalyzed cross-coupling reactions, see:
• 2a Fürstner A, Martin R. Chem. Lett. 2005; 34: 624
• 2b Sherry BD, Fürstner A. Acc. Chem. Res. 2008; 41: 1500
• 2c Czaplik WM, Mayer M, Cvengros J, von Wangelin AJ. ChemSusChem 2009; 2: 396

For reviews on iron-catalyzed reduction reactions, see:
• 3a Gaillard S, Renaud J.-L. ChemSusChem 2008; 1: 505
• 3b Morris RH. Chem. Soc. Rev. 2009; 38: 2282
• 3c Le Bailly BA. F, Thomas SP. RSC Adv. 2011; 1: 1435
• 3d Darwish M, Wills M. Catal. Sci. Technol. 2012; 2: 243
• 4 For a review on asymmetric iron catalysis, see: Gopalaiah K. Chem. Rev. 2013; 113: 3248

For hydroarylation reactions, see:
• 5a Li R, Wang SR, Lu W. Org. Lett. 2007; 9: 2219
• 5b Dal Zotto C, Wehbe J, Virieux D, Campagne J.-M. Synlett 2008; 2033
• 5c Komeyama K, Igawa R, Takaki K. Chem. Commun. 2010; 46: 1748

For carbometalation reactions, see:
• 5d Yamagami T, Shintani R, Shirakawa E, Hayashi T. Org. Lett. 2007; 9: 1045
• 6 Chan LY, Kim S, Park Y, Lee PH. J. Org. Chem. 2012; 77: 5239
• 7 Fürstner A, Majima K, Martín R, Krause H, Kattnig E, Goddard R, Lehmann CW. J. Am. Chem. Soc. 2008; 130: 1992

For reviews on synergistic metallo-organocatalysis, see:
• 8a Du Z, Shao Z. Chem. Soc. Rev. 2013; 42: 1337
• 8b Allen AE, MacMillan DW. C. Chem. Sci. 2012; 3: 633
• 8c Patil NT, Shinde VS, Gajula B. Org. Biomol. Chem. 2012; 10: 211
• 8d Zhong C, Shi X. Eur. J. Org. Chem. 2010; 2999
• 8e Shao Z, Zhang H. Chem. Soc. Rev. 2009; 38: 2745

For representative examples, see:
• 9a Zhou S, Fleischer S, Junge K, Beller M. Angew. Chem. Int. Ed. 2011; 50: 5120
• 9b Motoyama K, Ikeda M, Miyake Y, Nishibayashi Y. Eur. J. Org. Chem. 2011; 2239
• 10a Montaignac B, Vitale MR, Michelet V, Ratovelomanana-Vidal V. Org. Lett. 2010; 12: 2582
• 10b Montaignac B, Vitale MR, Ratovelomanana-Vidal V, Michelet V. J. Org. Chem. 2010; 75: 8322
• 10c Montaignac B, Vitale MR, Ratovelomanana-Vidal V, Michelet V. Eur. J. Org. Chem. 2011; 3723
• 10d Montaignac B, Östlund V, Vitale MR, Ratovelomanana-Vidal V, Michelet V. Org. Biomol. Chem. 2012; 10: 2300
• 10e Montaignac B, Praveen C, Vitale MR, Michelet V, Ratovelomanana-Vidal V. Chem. Commun. 2012; 48: 6559
• 10f Praveen C, Montaignac B, Vitale MR, Ratovelomanana-Vidal V, Michelet V. ChemCatChem 2013; 5: 2395

For seminal examples, see:
• 11a Binder JT, Crone B, Haug TT, Menz H, Kirsch SF. Org. Lett. 2008; 10: 1025
• 11b Yang T, Ferrali A, Campbell L, Dixon DJ. Chem. Commun. 2008; 2923

For related metallo-organocatalyzed cyclization reactions, see:
• 11c Bihelovic F, Matovic R, Vulovic B, Saicic RN. Org. Lett. 2007; 9: 5063
• 11d Vulovic B, Bihelovic F, Matovic R, Saicic RN. Tetrahedron 2009; 65: 10485
• 12a Melchiorre P. Angew. Chem. Int. Ed. 2012; 51: 9748
• 12b Xu L.-W, Luo J, Lu Y. Chem. Commun. 2009; 1807
• 12c Zhang L, Luo S. Synlett 2012; 23: 1575
• 13 Several metal-enolates are known to undergo this type of rearrangement. For a review, see: Dénès F, Pérez-Luna A, Chemla F. Chem. Rev. 2010; 110: 2366
• 14 Several attempts to react an internal alkyne analogue of 1, which possesses a methyl substituent in terminal position, led to complex reaction mixtures.