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Deaminative Arylation and Alkenyaltion of Aliphatic Tertiary Amines with Aryl and Alkenylboronic Acids via Nitrogen Ylides
Ist Teil von
Angewandte Chemie, 2022-12, Vol.134 (52), p.n/a
Ort / Verlag
Weinheim: Wiley Subscription Services, Inc
Erscheinungsjahr
2022
Link zum Volltext
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
Transition‐metal‐catalyzed Suzuki–Miyaura coupling has significantly advanced C−C bond formation and has been well recognized in organic synthesis, pharmaceuticals, materials science and other fields. In this rapid development, cross coupling without transition metal catalyst is a big challenge in this field, and using widely existing tertiary amines as electrophiles to directly couple with boronic acids has great hurdles yet significant application prospects. Herein, we report an efficient and general deaminative arylation and alkenylation of tertiary amines (propargyl amines, allyl amines and 1H‐indol‐3‐yl methane amines) with ary and alkenylboronic acids enabled by difluorocarbene under transition‐metal‐free conditions. Preliminary mechanism experiments suggest that in situ formed difluoromethyl quaternary amine salt, nitrogen ylide and tetracoordinate boron species are the key intermediates, the subsequent 1,2‐metallate shift and protodeboronation complete the new coupling reaction.
An efficient and general deaminative arylation and alkenylation of tertiary amines with aryl and alkenylboronic acids is enabled by difluorocarbene under transition‐metal‐free conditions. This protocol represents a novel reaction mode which succeeded in the construction of Csp3−Csp2 bonds via an in situ formed nitrogen ylide from tertiary amines (propargyl amines, allyl amines and 1H‐indol‐3‐yl methane amines) and difluorocarbene with aryl and alkenylboronic acids.