Recent Developments and Applications of the Chiral Brønsted Acid Catalyzed Allylboration of Carbonyl Compounds

Abstract

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

Catalytic asymmetric allylation of aldehydes with alkenes through allylic C(sp3)–H functionalization mediated by organophotoredox and chiral chromium hybrid catalysis

“…Additionally, the use of photocatalyst 11 , bearing a mesityl group instead of a xylyl group, did not negatively affect these results (entry 13). It is noteworthy that compared to traditional catalytic asymmetric carbonyl allylations,2 except for the Krische's method,2i,p this reaction can bypass the preactivation step of the nucleophile using stoichiometric metal species.…”

“…Catalytic asymmetric C(sp 3 )–H bond functionalization is an emerging synthetic method affording direct access to useful chiral building blocks from stable organic molecules 1. For example, catalytic asymmetric allylation of aldehydes using unactivated alkenes as pronucleophiles produces enantiomerically-enriched homoallylic alcohols, which act as versatile synthetic intermediates for numerous functional molecules, including various drug leads 2. The catalytic asymmetric carbonyl ene reaction is a representative example (Fig.…”

A Versatile Bis‐Allylboron Reagent for the Stereoselective Synthesis of Chiral Diols

“…Axially chiral phosphoric acids have shown to be effective in activating allyl, allenyl, and propargyl boronates in their reactions with aldehydes . Indeed, commercially available TRIP (Table ) exhibited asymmetric induction in the allyl transfer and the best reactivity profile among all examined catalysts (see Supporting Information for reaction optimization).…”

Enantioselective Total Synthesis of (−)‐Finerenone Using Asymmetric Transfer Hydrogenation

“…In order to understand the origin of the selectivity issues encountered we have carried out DFT [17,18] calculations (Gaussian 16 Revision A.03, [19] see the Supporting Information for further details) and determined the TSs for reaction of both atropisomers. Note that the Hantzsch ester was simplified to a methyl ester and the ethoxy group on 6 was replaced by a methoxy group.…”