Activation of Diboron Reagents with Bronsted Bases and Alcohols: An Experimental and Theoretical Perspective of the Organocatalytic Boron Conjugate Addition Reaction

Cristina Pubill-Ulldemolins, Amadeu Bonet, Carles Bo, Henrik Gulyas, Elena Fernandez

Research output: Contribution to journalArticle (Academic Journal)peer-review

107 Citations (Scopus)

Abstract

Bases play an important role in organocatalytic boron conjugate addition reactions. The sole use of MeOH and a base can efficiently transform acyclic and cyclic activated olefins into the corresponding beta-borated products in the presence of diboron reagents. Inorganic and organic bases deprotonate MeOH in the presence of diboron reagents. It is concluded, on the basis of theoretical calculations, NMR spectroscopic data, and ESI-MS experiments, that the methoxide anion forms a Lewis acidbase adduct with the diboron reagent. The sp2 B atom of the methoxidediboron adduct gains a strongly nucleophilic character, and attacks the electron-deficient olefin. The methanol protonates the intermediate, generating the product and another methoxide anion. This appears to be the simplest method to activate diboron reagents and make them suitable for incorporation into target organic molecules.

Original languageEnglish
Pages (from-to)1121-1126
Number of pages6
JournalChemistry - A European Journal
Volume18
Issue number4
DOIs
Publication statusPublished - Jan 2012

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