Stimulating excursions into organolead chemistry: modular domino sequences triggered by oxidative cleavage

• Published in: Tetrahedron: asymmetry Vol. 26; no. 18-19; pp. 981 - 1035
• Main Authors: Abet, Valentina, Castillo, Rafael R., Aquino, Maurizio, Gandara, Zoila, Arseniyadis, Siméon
• Format: Journal Article
• Language: English
• Published: Elsevier Ltd 15-10-2015
• ISSN: 0957-4166; 1362-511X
• DOI: 10.1016/j.tetasy.2015.08.001

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The present report intends to highlight the main lines of our investigation on a series of modular domino reactions focusing on a multi-task reagent, namely Pb(OAc)4 in conjunction with an olefin as a source of complexity. It covers the design, development, and mechanistic aspects of a domino methodology discovered in our laboratory, which presents numerous challenges, including issues of chemo-, regio-, and diastereoselectivities. The principal characteristic of the chemistry presented is the potential of creating cyclic arrays that can be suitably functionalized for subsequent conversion into various complex systems. The effects of systematic variation of domino promoter, substitution pattern, solvent, temperature, and microwave activation on the outcome of the domino reaction are presented. In general terms, the domino chemistry reported here could be conveniently divided into two categories, dealing with first and second generation domino probes based on the nature of the angular substituent, each of which will be addressed in turn. This review is not intended to give an extensive coverage of the various uses of Pb(OAc)4 in synthesis reported in the literature, but will expose relevant reactions where appropriate focusing exclusively on multi-stage transformations initiated by the reagent.