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Abstract:
Suzuki-type cross-coupling is one of the most common strategies for the construction of C-C bonds. Despite great progress on the preparation of C(sp(2))-C(sp(2)) bonds, C(sp(2))-C(sp(3)) cross-coupling with aliphatic halides remains rare, especially with tertiary aliphatic halides and under transition-metal-free conditions. Here we report an efficient C(sp(2))-C(sp(3)) cross-coupling between alpha-(pseudo)halo aliphatic ketones and arylboronic acids via a 1,4-metallate shift. The alpha-arylated ketones obtained from this protocol under transition-metal-free and additive-free conditions in the presence of base are formed when the key intermediate enolate traps the arylboronic acid, leading to a tetracoordinate boron intermediate. A subsequent 1,4-metallate shift affords the Suzuki-type coupling products. This strategy provides a practical, scalable and operationally straightforward method for the synthesis of C(sp(2))-C(sp(3)) bonds, and is compatible with challenging tertiary aliphatic halides, allowing for the preparation of 1,3-disubstituted target products.
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NATURE SYNTHESIS
ISSN: 2731-0582
Year: 2023
Issue: 12
Volume: 2
Page: 1211-1221
1 7 . 5
JCR@2023
1 7 . 5 0 0
JCR@2023
JCR Journal Grade:1
Cited Count:
SCOPUS Cited Count: 7
ESI Highly Cited Papers on the List: 0 Unfold All
WanFang Cited Count:
Chinese Cited Count:
30 Days PV: 0
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