Catalytic Asymmetric 1,2-Migration/Allylation of Alkynyl Boronate Complexes: A Modular Route to Enantioenriched Skipped 1,4-Dienes
Liang Wei, Zhuowen Guo, Jasper L. Tyler, Varinder K. Aggarwal
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.
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.
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Taxonomy
TopicsCatalytic C–H Functionalization Methods · Organoboron and organosilicon chemistry · Catalytic Cross-Coupling Reactions