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Mild Protocols for Generating Molecular Complexity: A Comparative Study of Hetero‐Domino Reactions Based on the Oxidant and the Substitution Pattern
Author(s) -
Candela Lena José I.,
Sánchez Fernández Elena M.,
Ramani Alwar,
Birlirakis Nicolas,
Barrero Alejandro F.,
Arseniyadis Siméon
Publication year - 2005
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400549
Subject(s) - domino , chemistry , pyridinium chlorochromate , pyridinium , reactivity (psychology) , allylic rearrangement , diol , redox , combinatorial chemistry , organic chemistry , medicinal chemistry , catalysis , medicine , alternative medicine , pathology
A bicyclic unsaturated 1,2‐diol framework was found to undergo an interesting set of domino reactions on treatment with oxidants. One‐pot syntheses of seven‐membered‐ring‐containing frameworks were achieved by a Pb(OAc) 4 ‐mediated domino process, while with other oxidants investigated, such as Mn(OAc) 3 , Dess–Martin periodinane, PhI(OAc) 2 , Ph 3 Bi(CO) 3 , NaIO 4 , and NaBiO 3 , the domino process was interrupted halfway through. Finally, tetrapropylammonium perruthenate (TPAP‐NMO), Pd(OAc) 2 , pyridinium dichromate (PDC), and pyridinium chlorochromate (PCC) gave only allylic oxidation and further diketone formation without any of the bond cleavage that is necessary to initiate the domino process. The substrates were chosen to test the limits of reactivity of various unsaturated 1,2‐diol derivatives and to provide guidelines for their use in constructing complex synthetic targets. In this article we provide details of the reaction conditions, preparation of the starting materials and characterization of the products, along with new, unpublished results. Information is assembled to facilitate comparison between the various oxidants, solvents and substitution patterns. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)