PdI₂-Catalyzed Synthesis of Heterocycles

Abstract

Some PdI₂-based complexes have proved to be efficient catalysts for the selective, atom-economical synthesis of different important heterocyclic derivatives starting from very simple building blocks, such as simple or functionalized alkynes, amino alcohols, diamines, carbon monoxide, carbon dioxide, alcohols, water, and oxygen. The synthetic protocols leading to heterocycles have been grouped into three classes of reactions: (a) cycloisomerization of (Z)-2-en-4-yn-1-ols, (Z)-2-en-4-yne-1-thiols, (Z)-(2-en-4-ynyl)amines, 2-alkynylbenzyl alcohols to give substituted furans, thiophenes, pyrroles, and 1,3-dihydroisobenzofurans or 1H-iso­chromenes, respectively; (b) oxidative carbonylation of simple alkynes, 1,5-diynes, functionalized alkynes bearing a suitably placed nucleophilic group, amino alcohols, and diamines to afford substituted maleic anhydrides, functionalized β- and γ-lactones, β- and γ-lactams, dihydroindol-2-ones, furans, pyrroles, thiophenes, tetrahydrofurans, oxazolidin-2-ones, oxazolines, cyclic ureas, 4H-3,1-benzoxazines, quinazolin-2-ones, quinolin-4-ones; (c) reductive carbonylation of alkynes to give substituted γ-lactones and ­formation of lactone or anhydride derivatives by additive carbonyl­ation, resulting from the combination between oxidative carbonyl­ation of the triple bond and reduction of a suitable functional group present in the substrate itself.

• 1. Introduction

• 2. Synthesis of Heterocycles by PdI₂-Catalyzed Cycloiso­merization Reactions

• 3. Synthesis of Heterocycles by PdI₂-Catalyzed Oxidative Carbonylation Reactions

• 3.1 PdI₂-Catalyzed Oxidative Cyclocarbonylation of Simple and Functionalized Alkynes

• 3.2 PdI₂-Catalyzed Oxidative Cyclization-Dialkoxycarbonyl­ation of 1,5-Diynes

• 3.3 PdI₂-Catalyzed Oxidative Cyclization-Alkoxycarbonyl­ation of Functionalized Alkynes

• 3.4 PdI₂-Catalyzed Oxidative Monoaminocarbonylation of Alkynols

• 3.5 PdI₂-Catalyzed Oxidative Cyclocarbonylation of β-Amino Alcohols, 2-Aminophenols and Aromatic Diamines

• 4. Synthesis of Heterocycles by PdI₂-Catalyzed Additive and Reductive Carbonylation Reactions

• 5. Conclusions

Key words

carbonylation - cyclization - heterocycles - homogeneous catalysis - palladium

References

• 1 Pozharskii AF. Soldatenkov AT. Katritzky AR. Heterocycles in Life and Society   John Wiley and Sons; Chichester: 1997. 
• 2 Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry   Pergamon; Oxford: 2000. 
• For reviews on recent advances in the synthesis of furans, thiophenes, and pyrroles see:
• 3a Ferreira VF. de Souza MCVB. Cunha AC. Pereira LOR. Ferreira MLG. Org. Prep. Proced. Int.  2001,  33:  411 
• 3b Gilchrist TL. J. Chem. Soc., Perkin Trans. 1  1999,  2849 
• 3c Hou XL. Cheung HY. Hon TY. Kwan PL. Lo TH. Tong SY. Wong HNC. Tetrahedron  1998,  54:  1955 
• 4 For a recent review on the importance of the development of new atom-economical processes, see: Trost BM. Acc. Chem. Res.  2002,  35:  695 
• 5 For a recent account on transition metal-catalyzed cycloisomerizations, see: Trost BM. Krische MJ. Synlett  1998,  1 
• 6a Gabriele B. Salerno G. Lauria E. J. Org. Chem.  1999,  64:  7687 
• 6b Gabriele B. Salerno G. Chem. Commun.  1997,  1083 
• 7 Gabriele B. Salerno G. Fazio A. Org. Lett.  2000,  2:  351 
• 8a Gabriele B. Salerno G. Fazio A. J. Org. Chem.  2003,  68:  7853 
• 8b Gabriele B. Salerno G. Fazio A. Bossio MR. Tetrahedron Lett.  2001,  42:  1339 
• 9 Gabriele B. Salerno G. Fazio A. Pittelli R. Tetrahedron  2003,  59:  6251 
• 10 Sammes PG. Weller DJ. Synthesis  1995,  1205 
• 11 Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley-Interscience; New York: 2002. 
• 12a Gabriele B. Costa M. Salerno G. Chiusoli GP. J. Chem. Soc., Perkin Trans. 1  1994,  83 
• 12b Gabriele B. Costa M. Salerno G. Chiusoli GP. J. Chem. Soc., Chem. Commun.  1992,  1007 
• 13 Gabriele B. Veltri L. Salerno G. Costa M. Chiusoli GP. Eur. J. Org. Chem.  2003,  1722 
• 14a Gabriele B. Salerno G. De Pascali F. Costa M. Chiusoli GP. J. Chem. Soc., Perkin Trans. 1  1997,  147 
• 14b Gabriele B. Costa M. Salerno G. Chiusoli GP. J. Chem. Soc., Chem. Commun.  1994,  1429 
• 15 Bonardi A. Costa M. Gabriele B. Salerno G. Chiusoli GP. Tetrahedron Lett.  1995,  36:  7495 
• 16 Gabriele B. Salerno G. Veltri L. Costa M. Massera C. Eur. J. Org. Chem.  2001,  4607 
• 17a Fazio A. Gabriele B. Salerno G. Destri S. Tetrahedron  1999,  55:  485 
• 17b Paganuzzi V. Guattieri P. Riccardi P. Sacchelli T. Barberá J. Costa M. Dalcanale E. Eur. J. Org. Chem.  1999,  1527 
• 18a Destri S. Giovanella U. Fazio A. Porzio W. Gabriele B. Zotti G. Org. Electron.  2002,  3:  149 
• 18b Destri S. Porzio W. Meinardi F. Tubino R. Salerno G. Macromolecules  2003,  36:  273 
• 19 Gabriele B. Salerno G. De Pascali F. Costa M. Chiusoli GP. J. Organomet. Chem.  2000,  594:  409 
• 20 Baldwin JE. J. Chem. Soc., Chem. Commun.  1976,  734 
• 21a Gabriele B. Salerno G. De Pascali F. Costa M. Chiusoli GP. J. Org. Chem.  1999,  64:  7693 
• 21b Gabriele B. Salerno G. De Pascali F. Tomasi Scianò G. Costa M. Chiusoli GP. Tetrahedron Lett.  1997,  38:  6877 
• 22 Bacchi A. Costa M. Gabriele B. Pelizzi P. Salerno G. J. Org. Chem.  2002,  67:  4450 
• 23 Costa M. Della Cà N. Gabriele B. Massera C. Salerno G. Soliani M. J. Org. Chem.  2004,  69:  2469 
• 24 Bacchi A. Chiusoli GP. Costa M. Sani C. Gabriele B. Salerno G. J. Organomet. Chem.  1998,  562:  35 
• 25 Gabriele B. Salerno G. Fazio A. Campana FB. Chem. Commun.  2002,  1408 
• 26a Chiusoli GP. Costa M. Gabriele B. Salerno G. J. Mol. Catal. A: Chem.  1999,  143:  297 
• 26b Bacchi A. Chiusoli GP. Costa M. Gabriele B. Righi C. Salerno G. Chem. Commun.  1997,  1209 
• 27 Bacchi A. Costa M. Della Cà N. Fabbricatore M. Fazio A. Gabriele B. Nasi C. Salerno G. Eur. J. Org. Chem.  2004,  574 
• 28 Gabriele B. Salerno G. Veltri L. Costa M. J. Organomet. Chem.  2001,  622:  84 
• 29 Tsuji J. Takahashi M. Takahashi T. Tetrahedron Lett.  1980,  21:  849 
• 30 Gabriele B. Salerno G. Plastina P. Lett. Org. Chem.  2004,  1:  136 
• 31 Gabriele B. Salerno G. Plastina P. Costa M. Crispini A. Adv. Synth. Catal.  2004,  346:  351 
• 32 Gabriele B. Mancuso R. Salerno G. Costa M. J. Org. Chem.  2003,  68:  601 
• 33 Gabriele B. Salerno G. Brindisi D. Costa M. Chiusoli GP. Org. Lett.  2000,  2:  625 
• 34a Gabriele B. Mancuso R. Salerno G. Costa M. Chem. Commun.  2003,  486 
• 34b Gabriele B. Salerno G. Mancuso R. Costa M. J. Org. Chem.  2004,  69:  4741 
• 35 Chiusoli GP. Costa M. Pergreffi P. Riverberi S. Salerno G. Gazz. Chim. Ital.  1985,  115:  691 
• 36 Gabriele B. Salerno G. Costa M. Chiusoli GP. J. Organomet. Chem.  1995,  503:  21 
• 37 Bonardi A. Costa M. Gabriele B. Salerno G. Chiusoli GP. J. Chem. Soc., Chem. Commun.  1994,  2429 
• 38 Costa M. De Souza Santos L. Chiusoli GP. Gabriele B. Salerno G. J. Mol. Catal.  1993,  78:  151 
• 39 Gabriele B. Salerno G. Costa M. Chiusoli GP. Tetrahedron Lett.  1999,  40:  989 
• 40a Chiusoli GP. Costa M. Cucchia L. Gabriele B. Salerno G. Veltri L. J. Mol. Catal. A: Chem.  2003,  204:  133 
• 40b Gabriele B. Salerno G. Costa M. Chiusoli GP. Chem. Commun.  1999,  1381