Enantiospecific sp²-sp³ coupling of secondary and tertiary boronic esters

Bonet, Amadeu; Odachowski, Marcin; Leonori, Daniele; Essafi, Stephanie; Aggarwal, Varinder K.

Abstract

The cross-coupling of boronic acids and related derivatives with sp² electrophiles (the Suzuki–Miyaura reaction) is one of the most powerful C–C bond formation reactions in synthesis, with applications that span pharmaceuticals, agrochemicals and high-tech materials. Despite the breadth of its utility, the scope of this Nobel prize-winning reaction is rather limited when applied to aliphatic boronic esters. Primary organoboron reagents work well, but secondary and tertiary boronic esters do not (apart from a few specific and isolated examples). Through an alternative strategy, which does not involve using transition metals, we have discovered that enantioenriched secondary and tertiary boronic esters can be coupled to electron-rich aromatics with essentially complete enantiospecificity. As the enantioenriched boronic esters are easily accessible, this reaction should find considerable application, particularly in the pharmaceutical industry where there is growing awareness of the importance of, and greater clinical success in, creating biomolecules with three-dimensional architectures.

Citation

Bonet, A., Odachowski, M., Leonori, D., Essafi, S., & Aggarwal, V. K. (2014). Enantiospecific sp²-sp³ coupling of secondary and tertiary boronic esters. Nature Chemistry, 6(7), 584-589. https://doi.org/10.1038/nchem.1971

• Journal Article Type: Article
• Acceptance Date: Apr 30, 2014
• Online Publication Date: Jun 8, 2014
• Publication Date: 2014-07
• Deposit Date: Jul 13, 2016
• Publicly Available Date: Jul 13, 2016
• Journal: Nature chemistry
• Print ISSN: 1755-4330
• Electronic ISSN: 1755-4349
• Publisher: Nature Publishing Group
• Peer Reviewed: Peer Reviewed
• Volume: 6
• Issue: 7
• Pages: 584-589
• DOI: https://doi.org/10.1038/nchem.1971
• Keywords: Synthetic chemistry methodology
• Public URL: https://hull-repository.worktribe.com/output/440882
• Publisher URL: http://www.nature.com/nchem/journal/v6/n7/full/nchem.1971.html
• Additional Information: This is the authors accepted manuscript of an article published in: Nature chemistry, 2014, v.6.
• Contract Date: Jul 13, 2016