Synthesis of Acyclic Polycarbonyl Compounds via Ozonolysis of Cyclohexa-1,4-dienes

Abstract

Cobalt-catalyzed Diels–Alder reaction of 2-(trimethylsil­oxy)buta-1,3-dienes with alkynes gives substituted cyclohex-3-en-1-ones that were converted into polycarbonyl derivatives upon ozonolysis. Wittig olefination of ketoaldehydes gave unsaturated polycarbonyl derivatives or alternatively the ketoaldehydes were reacted with primary and secondary amines to give vinylogous amides. 2,7-Didiazo-1-phenylnonane-1,3,6,8-tetraone underwent double diazo-transfer reaction at the 1,3-dicarbonyl subunits by rhodium-catalyzed cyclization to give the cyclohex-2-ene-1,4-dione backbone.

Key words

cobalt - Diels–Alder - ozonolysis - polycarbonyls - Wittig olefination

• References


For some selected examples see:
• 1a Amat M, Griera R, Fabregat R, Molins E, Bosch J. J. Org. Chem. 2010; 75: 3797
• 1b Calo F, Richardson F, Barrett AG. M. Org. Lett. 2009; 11: 4910
• 1c Amat M, Griera R, Fabregat R, Molins E, Bosch J. Angew. Chem. Int. Ed. 2008; 47: 3348
• 1d Rubin MB, Gleiter R. Chem. Rev. 2000; 100: 1121
• 1e Griffin DA, Leeper FJ, Staunton J. J. Chem. Soc., Perkin Trans. 1 1984; 1035
• 2 Tarun EI, Rubinov DB, Metelitza DI. Appl. Biochem. Microbiol. 2005; 41: 12
• 3a Kersten L, Hilt G. Adv. Synth. Catal. 2012; 354: 863
• 3b Hilt G, Arndt M, Weske D. Synthesis 2010; 1321
• 3c Kersten L, Roesner S, Hilt G. Org. Lett. 2010; 12: 4920
• 3d Hilt G, Weske DF. Chem. Soc. Rev. 2009; 38: 3082
• 4a Hilt G. Chem. Rec. 2014; 14: 386
• 4b Hilt G. Synlett 2011; 1654
• 4c Hilt G, Korn TJ. Tetrahedron Lett. 2001; 42: 2783
• 4d Hilt G, du Mesnil F.-X, Lüers S. Angew. Chem. Int. Ed. 2001; 40: 387
• 5a Kuttner JR, Warratz S, Hilt G. Synthesis 2010; 1293
• 5b Hilt G, Smolko KI, Lotsch BV. Synlett 2002; 1081
• 6 Erver F, Kuttner JR, Hilt G. J. Org. Chem. 2012; 77: 8375
• 7 Maryanoff BE, Reitz AB. Chem. Rev. 1989; 89: 863
• 8a Zhou CC, Hill DR. Magn. Reson. Chem. 2007; 45: 128
• 8b Raczynska ED, Kosinska W, Osmialowski B, Gawinecki R. Chem. Rev. 2005; 105: 3561
• 8c Rappoport Z. The Chemistry of Enols . Wiley; Chichester: 1990
• 9a Mehta G, Muthusamy S. Tetrahedron 2002; 58: 9477
• 9b Hodgson DM, Pierard FY. T. M, Stupple PA. Chem. Soc. Rev. 2001; 30: 50
• 9c Singh VK, DattaGupta A, Sekar G. Synthesis 1997; 137
• 9d Li A.-H, Dai L.-X, Aggarwal VK. Chem. Rev. 1997; 97: 2341
• 9e Ishiguro K, Ikeda M, Sawaki Y. J. Org. Chem. 1992; 57: 3057
• 9f Padwa A, Hornbuckle SF. Chem. Rev. 1991; 91: 263

For preparation of Rh₂(OPiv)₄(H₂O)₂ see:
• 10a Cotton FA, Felthouse TR. Inorg. Chem. 1980; 19: 323

For ruthenium-catalyzed reaction, see:
• 10b Del Zotto A, Baratta W, Verardo G, Rigo P. Eur. J. Org. Chem. 2000; 2795
• 10c Li G.-Y, Che C.-M. Org. Lett. 2004; 6: 1621