0000000001318635
AUTHOR
Matthew N. Grayson
ω-Alkenylallylboronates: Design, Synthesis, and Application to the Asymmetric Allylation/RCM Tandem Sequence
P. B. thanks the Spanish MINECO for a Ramón y Cajal contract (RyC-2016-20951). M.N.G. thanks the University of Bath for financial support.
Recent developments and applications of the chiral Brønsted acid catalyzed allylboration of carbonyl compounds
The 50-year-old allylboration reaction has seen dramatic developments since the dawn of the new century after the first catalytic asymmetric versions came into play. In the past decade alone, several methodologies capable of achieving the desired homoallylic alcohols in over 90% ee have been developed. This review focuses on the chiral Brønsted acid catalyzed allylboration reaction, covering everything from the very first examples and precedents to modern day variations and applications.1 Introduction2 Early Developments3 Synthetic Applications4 Variants5 Computational Contribution6 Conclusions
Chiral Brønsted Acid-Catalyzed Asymmetric Allyl(propargyl)boration Reaction of ortho-Alkynyl Benzaldehydes: Synthetic Applications and Factors Governing the Enantioselectivity
Chiral Bronsted 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 dep…
CCDC 1434367: Experimental Crystal Structure Determination
Related Article: Elsa Rodríguez, Matthew N. Grayson, Amparo Asensio, Pablo Barrio, K. N. Houk, and Santos Fustero|2016|ACS Catalysis|6|2506|doi:10.1021/acscatal.6b00209
CCDC 1434366: Experimental Crystal Structure Determination
Related Article: Elsa Rodríguez, Matthew N. Grayson, Amparo Asensio, Pablo Barrio, K. N. Houk, and Santos Fustero|2016|ACS Catalysis|6|2506|doi:10.1021/acscatal.6b00209