# Catalytic Asymmetric 1,2-Migration/Allylation of Alkynyl Boronate Complexes: A Modular Route to Enantioenriched Skipped 1,4-Dienes

## TL;DR

This paper presents a new method to efficiently create complex diene structures with high selectivity using iridium catalysis.

## Contribution

A novel Ir-catalyzed 1,2-migration/allylation strategy for enantioselective synthesis of skipped 1,4-dienes.

## Key findings

- High regio-, diastereo-, and enantioselectivity achieved in the synthesis of skipped 1,4-dienes.
- Alkenylboron intermediates enable access to tetrasubstituted alkene-containing dienes.
- The method offers a modular route to complex natural product motifs.

## Abstract

Stereodefined skipped 1,4-dienes are key structural motifs
found
in a wide range of natural products and bioactive molecules. However,
their stereo- and enantioselective syntheses remain a significant
challenge. While electrophilic-allylation-triggered 1,2-migration
reactions of alkynyl boronate complexes are in principle a straightforward
method to produce skipped dienes, such reactions suffer from poor
stereoselectivity or undesired regioselectivity. We now report that,
through judicious selection of the alkynyl boronate complex, we can
achieve a highly regio-, diastereo-, and enantioselective construction
of polysubstituted skipped 1,4-dienes via an Ir-catalyzed 1,2-migration/allylation
strategy. Furthermore, the resulting alkenylboron species could be
intercepted, which provides a gateway to even more challenging tetrasubstituted
alkene-containing skipped dienes.