Chiral Brønsted acid-catalyzed allyl(propargyl)boration of ortho-alkynyl benzaldehydes gives rise to ω-alkynyl homoallylic(homopropargylic)alcohols that can be further transformed to complex molecular scaffolds via subsequent hydroalkoxylation, ring-closing enyne metathesis (RCEYM), or intramolecular Pauson-Khand reaction (PKR). Optimizations of each two-step transformation is reported. A strong dependence between enantioselectivities and the nature of the substitution at the alkynyl moiety is observed, showcasing that the triple bond is not merely a spectator in this transformation. Density functional theory (DFT) calculations (M06-2X/6-311+G(d,p)-IEFPCM//B3LYP/6-31G(d)) show that this dependence is the result of the steric and electronic properties of the alkyne substituent.
- asymmetric allylboration
- chiral Brønsted acids
- DFT calculations
- diversity-oriented synthesis
ASJC Scopus subject areas
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- Department of Chemistry - Senior Lecturer
- EPSRC Centre for Doctoral Training in Advanced Automotive Propulsion Systems (AAPS CDT)
Person: Research & Teaching, Affiliate staff