Work

Simultaneous Installation of 1,6-Stereocenters by Asymmetric Allylation of Resorcinol Boronates: Application to the Synthesis of Merocyclophane A

Year: 2026

Type: article

Abstract: Installing multiple noncontiguous stereocenters in a single catalytic event offers a powerful platform for constructing complex three-dimensional molecular architectures, yet asymmetric methodologies capable of selectively forging remote 1,n-stereochemical relationships remain limited. Here we disclose a strategy for the simultaneous installation of 1,6-stereocenters via para-selective activation of chiral resorcinol boronates with π-allyl iridium complexes. Upon oxidation-induced rearomatization, the resulting dearomatized intermediates furnish the allylated products in an overall transformation that exhibits excellent regio- and stereoselectivity. Crucially, independent variation of the ligand and boronic ester configuration provides predictable access to all four stereoisomers with no observable match-mismatch effects. The synthetic potential of the methodology is exemplified by a concise total synthesis of the cyanobacteria-derived [7.7]paracyclophane merocyclophane A, in which all stereocenters are installed simultaneously on the resorcinol core in a single step.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.6c14045

Authors: Ze-Shu Wang, Joshua D. Mitchell, Jasper L. Tyler, Laura J. McCormick McPherson, Simon J. Coles, Varinder K. Aggarwal

Institutions: University of Bristol, University of Southampton

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: University of Southampton, University of Bristol, Engineering and Physical Sciences Research Council